JP5577069B2 - Hexacoordinate ruthenium or osmium metal carbene metathesis catalyst - Google Patents

Description

  The present invention relates to novel hexacoordinated metathesis catalysts and methods for their production and use.

  Metathesis catalysts include, for example, U.S. Pat.Nos. 5,312,940, 5,342,909, 5,728,917, 5,750,815, 5,710,298 and 5,831,108, and PCT Publications WO 97/20865 and WO 97 /. No. 29135, previously described, all of which are hereby incorporated by reference. These publications describe well-defined single component ruthenium or osmium catalysts with several advantageous properties. For example, these catalysts are tolerant to various functional groups and are generally more active than previously known metathesis catalysts. Recently, in these metal-carbene complexes, U.S. Patent Application Nos. 09 / 539,840, 09 / 576,370 and PCT Publication No. WO 99/51344, the contents of each of which are incorporated herein by reference. The inclusion of N-heterocyclic carbene (NHC) ligands such as imidazolidine ligands or triazolylidene ligands described in Has been found to improve. In unexpectedly surprising results, it has been found that changing the structure from a well-established five-coordinate catalyst structure to a six-coordinate catalyst structure significantly improves the properties of the catalyst. For example, these hexacoordination catalysts of the present invention include not only ring-closing metathesis (`` RCM '') reactions, but also cross-metathesis (`` CM '') reactions, acyclic olefin reactions, and ring-opening metathesis polymerization (`` ROMP ''). It also shows increased activity and selectivity in other metathesis reactions such as) reaction.

U.S. Pat.No. 5,312,940 U.S. Pat.No. 5,342,909 U.S. Pat.No. 5,728,917 U.S. Pat.No. 5,750,815 U.S. Patent No. 5,710,298 U.S. Pat.No. 5,831,108 PCT Publication No. WO 97/20865 PCT Publication No. WO 97/29135 U.S. Patent Application No. 09 / 539,840 U.S. Patent Application No. 09 / 576,370 PCT Publication No.WO 99/51344

  The present invention relates to a novel hexacoordinated metathesis catalyst and methods for making and using the same.

The catalyst of the present invention has the formula:

(Where
M is ruthenium or osmium;
X and X ¹ may be the same or different and each is independently an anionic ligand;
L, L ^{1 ′} and L ² may be the same or different and each is independently a neutral electron donor ligand; and
R and R ¹ are each independently hydrogen or C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C ₁ -C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl, C ₁ -C ₂₀ alkylsulfinyl, and silyl A substituent selected from the group consisting of
belongs to. Optionally, each of the R or R ¹ substituents is each further substituted with one or more groups selected from halogen, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, and phenyl. It may be substituted with one or more groups selected from the group consisting of C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, and aryl. Further, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include, but are not limited to, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, Carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

In a preferred embodiment, L ² and L ^{1 ′} are pyridine and L is a phosphine or N-heterocyclic carbene ligand. Examples of N-heterocyclic carbene ligands include:

Wherein R, R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen or C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C ₁ -C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ - C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl, C ₁ -C ₂₀ alkylsulfinyl, and substituents selected from the group consisting of silyl)
Is mentioned. Optionally, each of the R, R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ substituents is halogen, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, and Substituted with one or more groups selected from the group consisting of C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, and aryl, each optionally further substituted with one or more groups selected from phenyl May be. Further, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include, but are not limited to, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, Carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

  It has been found that inclusion of NHC ligands in hexacoordinated ruthenium or osmium catalysts dramatically improves the properties of these complexes. NHC-based hexacoordination complexes are very active, which significantly reduces the amount of catalyst required.

  The present invention relates generally to ruthenium and osmium carbene catalysts for use in olefin metathesis reactions. More specifically, the present invention relates to hexacoordinated ruthenium and osmium carbene catalysts and methods for making and using the same. The terms “catalyst” and “complex” are used interchangeably herein.

(式中、
Mはルテニウム又はオスミウムであり；
X及びX¹は各々独立に陰イオン性配位子であり；
L及びL¹は各々独立に任意の中性電子供与配位子であり；
R及びR¹は同一であっても異なっていてもよく、各々独立に水素又はC₁-C₂₀アルキル、C₂-C₂₀アルケニル、C₂-C₂₀アルキニル、アリール、C₁-C₂₀カルボキシレート、C₁-C₂₀アルコキシ、C₂-C₂₀アルケニルオキシ、C₂-C₂₀アルキニルオキシ、アリールオキシ、C₂-C₂₀アルコキシカルボニル、C₁-C₂₀アルキルチオ、C₁-C₂₀アルキルスルホニル、C₁-C₂₀アルキルスルフィニル、及びシリルからなる群より選択される置換基である)
のものである。必要に応じて、R又はR¹置換基の各々は、ハロゲン、C₁-C₅アルキル、C₁-C₅アルコキシ、及びフェニルから選択される1個以上の基で各々がさらに置換されていてもよいC₁-C₁₀アルキル、C₁-C₁₀アルコキシ、及びアリールからなる群より選択される1個以上の基で置換されていてもよい。さらに、この触媒配位子はいずれも、1個以上の官能基をさらに含んでもよい。好適な官能基の例としては、限定されるものではないが、ヒドロキシル、チオール、チオエーテル、ケトン、アルデヒド、エステル、エーテル、アミン、イミン、アミド、ニトロ、カルボン酸、ジスルフィド、カルボナート、イソシアネート、カルボジイミド、カルボアルコキシ、カルバメート、ハロゲン、アルコール、スルホン酸、ホスフィン、イミド、アセタール、ケタール、ボロネート、シアノ、シアノヒドリン、ヒドラジン、エナミン、スルホン、スルフィド、及びスルフェニルが挙げられる。 Unmodified ruthenium and osmium carbene complexes are disclosed in U.S. Pat.Nos. 5,312,940, 5,342,909, 5,728,917, 5,750,815, and 5,710,298, all of which are incorporated herein by reference. It is described in. The ruthenium and osmium carbene complexes disclosed in these patents all have a metal center in the +2 oxidation state, have 16 electrons, and are pentacoordinate. These catalysts have the general formula:

(Where
M is ruthenium or osmium;
X and X ¹ are each independently an anionic ligand;
L and L ¹ are each independently any neutral electron donor ligand;
R and R ¹ may be the same or different and are each independently hydrogen or C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C ₁ -C ₂₀ carboxy rate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl , C ₁ -C ₂₀ alkylsulfinyl, and a substituent selected from the group consisting of silyl)
belongs to. Optionally, each of the R or R ¹ substituents is each further substituted with one or more groups selected from halogen, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, and phenyl. It may be substituted with one or more groups selected from the group consisting of C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, and aryl. Further, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include, but are not limited to, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, Carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

(式中、
Mはルテニウム又はオスミウムであり；
X及びX¹は同一であっても異なっていてもよく、各々独立に任意の陰イオン性配位子であり；
L、L^1'及びL²は同一であっても異なっていてもよく、各々独立に任意の中性電子供与配位子であり；
R及びR¹は同一であっても異なっていてもよく、各々独立に水素又はC₁-C₂₀アルキル、C₂-C₂₀アルケニル、C₂-C₂₀アルキニル、アリール、C₁-C₂₀カルボキシレート、C₁-C₂₀アルコキシ、C₂-C₂₀アルケニルオキシ、C₂-C₂₀アルキニルオキシ、アリールオキシ、C₂-C₂₀アルコキシカルボニル、C₁-C₂₀アルキルチオ、C₁-C₂₀アルキルスルホニル、C₁-C₂₀アルキルスルフィニル、及びシリルからなる群より選択される置換基である)
のものである。必要に応じて、R又はR¹置換基の各々は、ハロゲン、C₁-C₅アルキル、C₁-C₅アルコキシ、及びフェニルから選択される1個以上の基で各々がさらに置換されていてもよいC₁-C₁₀アルキル、C₁-C₁₀アルコキシ、及びアリールからなる群より選択される1個以上の基で置換されていてもよい。さらに、この触媒配位子はいずれも、1個以上の官能基をさらに含んでもよい。好適な官能基の例としては、限定されるものではないが、ヒドロキシル、チオール、チオエーテル、ケトン、アルデヒド、エステル、エーテル、アミン、イミン、アミド、ニトロ、カルボン酸、ジスルフィド、カルボナート、イソシアネート、カルボジイミド、カルボアルコキシ、カルバメート、ハロゲン、アルコール、スルホン酸、ホスフィン、イミド、アセタール、ケタール、ボロネート、シアノ、シアノヒドリン、ヒドラジン、エナミン、スルホン、スルフィド、及びスルフェニルが挙げられる。 The catalysts of the present invention are similar in that they are Ru or Os complexes; however, in these catalysts, the metal is in the +2 oxidation state, has 18 electrons, is hexacoordinated is there. These catalysts have the general formula:

(Where
M is ruthenium or osmium;
X and X ¹ may be the same or different and are each independently any anionic ligand;
L, L ^{1 ′} and L ² may be the same or different and are each independently any neutral electron donor ligand;
R and R ¹ may be the same or different and are each independently hydrogen or C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C ₁ -C ₂₀ carboxy rate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl , C ₁ -C ₂₀ alkylsulfinyl, and a substituent selected from the group consisting of silyl)
belongs to. Optionally, each of the R or R ¹ substituents is each further substituted with one or more groups selected from halogen, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, and phenyl. It may be substituted with one or more groups selected from the group consisting of C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, and aryl. Further, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include, but are not limited to, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, Carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

Hexacoordination complexes offer several advantages over known pentacoordination complexes. For example, hexacoordination complexes are saturated in coordination and thus have greater air stability in the solid state. Due to the lability of added ligands such as pyridine, this complex starts faster than the pentacoordinated species based on phosphine. Slow onset means that only a fraction of the complex is actually catalytically active. This wastes much of the added complex. Faster initiators can reduce the amount of catalyst input. Furthermore, and without being bound by theory, polycoordinating complexes (polydisperity) have a tendency to recombine with unstable ligands compared to phosphine due to slow propogation. ) Is slower. Furthermore, coordinately saturated species crystallize better than their pentacoordinate equivalents. In addition, due to the instability of ligands (e.g. pyridine and chlorine) in hexacoordination complexes, these complexes make it possible to obtain previously difficult complexes and through different means. To provide higher purity specific complexes that can be obtained. For example, pentacoordinate benzylidene having triphenylphosphine as a phosphine ligand can be produced with higher yield and higher purity using a hexacoordination complex. Pentacoordinate benzylidene with P (p-CF ₃ C ₆ H ₄ ) ₃ as the phosphine ligand is not available through existing means. Without being bound by theory, it is believed that it is necessary to replace a strong donor ligand with a weak donor ligand. The substitution of the anionic ligand of a hexacoordinated complex is much faster than in the corresponding pentacoordinated species (eg phosphine bond). Without being bound by theory, it is believed that this is because the ligand must be dissociated before the anionic ligand is replaced. Complexes that rapidly dissociate their neutral electron donating ligand will undergo faster substitution.

により示されるような、金属中心に結合した少なくとも1個のNHC配位子を有する。本発明の触媒の好ましい実施形態においては、R置換基は水素であり、R¹置換基はC₁-C₂₀アルキル、C₂-C₂₀アルケニル、及びアリールからなる群より選択される。さらにより好ましい実施形態においては、R¹置換基は、必要に応じてC₁-C₅アルキル、C₁-C₅アルコキシ、フェニル、及び1個の官能基からなる群より選択される1個以上の基で置換されていてもよいフェニル又はビニルである。特に好ましい実施形態においては、R¹置換基は、クロリド、ブロミド、ヨージド、フルオリド、-NO₂、-NMe₂、メチル、メトキシ及びフェニルからなる群より選択される1個以上の基で置換されたフェニル又はビニルである。最も好ましい実施形態においては、R¹置換基はフェニル又は-C=C(CH₃)₂である。R¹がビニルである場合、この触媒は一般式：

(式中、M、L、L¹、L^1'、L²、X、X¹、及びRは上記で定義された通りである)
のものである。R'及びR''は好ましくは独立に水素又はフェニルであるが、R又はR¹について列挙された基のいずれかから選択してもよい。 The catalysts of the present invention are also useful for ring opening metathesis polymerization (ROMP), ring closure metathesis (RCM), ADMET, and cross metathesis. The synthesis and polymerization of olefins via these metathesis reactions are described, for example, in U.S. Patent Application No. 09 / 891,144 entitled `` Synthesis of Functionalized and Unfunctionalized Olefins '' filed June 25, 2001, and U.S. Patent Application No. 09 / 491,800, the contents of each of which are hereby incorporated by reference. A preferred embodiment of the catalyst of the present invention has the general formula:

Having at least one NHC ligand attached to the metal center, as shown by In a preferred embodiment of the catalyst of the present invention, the R substituent is hydrogen and the R ¹ substituent is selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, and aryl. In an even more preferred embodiment, the R ¹ substituent is optionally one or more selected from the group consisting of C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, phenyl, and one functional group. Or phenyl or vinyl which may be substituted with In particularly preferred embodiments, the R ¹ substituent is substituted with one or more groups selected from the group consisting of chloride, bromide, iodide, fluoride, —NO ₂ , —NMe ₂ , methyl, methoxy and phenyl. Phenyl or vinyl. In the most preferred embodiment, the R ¹ substituent is phenyl or —C═C (CH ₃ ) ₂ . When R ¹ is vinyl, the catalyst has the general formula:

(Wherein M, L, L ¹ , L ^{1 ′} , L ² , X, X ¹ , and R are as defined above)
belongs to. R ′ and R ″ are preferably independently hydrogen or phenyl, but may be selected from any of the groups listed for R or R ¹ .

In a preferred embodiment of the invention, X and X ¹ are each independently hydrogen, halide, or the following groups: C ₁ -C ₂₀ alkyl, aryl, C ₁ -C ₂₀ alkoxide, aryl oxide, C ₃ -C ₂₀ Alkyl diketonates, aryl diketonates, C ₁ -C ₂₀ carboxylates, aryl sulfonates, C ₁ -C ₂₀ alkyl sulfonates, C ₁ -C ₂₀ alkyl thios, C ₁ -C ₂₀ alkyl sulfonyls, or C _1- it is one to C ₂₀ alkylsulfinyl. If necessary, X and X ¹ is halogen, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, and further substituted C ₁ optionally -C with one or more groups selected from phenyl ₁₀ It may be substituted with one or more groups selected from the group consisting of alkyl, C ₁ -C ₁₀ alkoxy, and aryl. In more preferred embodiments, X and X ¹ are halide, benzoate, C ₁ -C ₅ carboxylate, C ₁ -C ₅ alkyl, phenoxy, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkylthio, aryl, and C ₁ -C ₅ alkyl sulfonate. In an even more preferred embodiment, X and X ¹ are each halide, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, ( CF ₃ ) (CH ₃ ) ₂ CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate. In the most preferred embodiment, X and X ¹ are each chloride.

L, L ¹ , L ^{1 ′} and L ² may be any suitable monodentate or multidentate neutral electron donor ligand. Examples of the multidentate neutral electron donor ligand include a bidentate, tridentate, or tetradentate neutral electron donor ligand. In a preferred embodiment of the catalyst of the present invention, L, L ¹ , L ^{1 ′} and L ² are each independently phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine. , Sulfoxide, carboxyl, nitrosyl, pyridine, and thioether, or any derivative thereof. At least one of L, L ¹ , L ^{1 ′} and L ² may also be an N-heterocyclic carbene ligand. Preferred embodiments include complexes where L ^{1 ′} and L ² are NHC ligands which may be the same or different.

In a preferred embodiment, at least one of L, L ¹ , L ^{1 ′} and L ² has the formula PR ³ R ⁴ R ⁵ , wherein R ³ , R ⁴ and R ⁵ are each independently aryl or C ₁ -C ₁₀ alkyl, in particular primary alkyl, secondary phosphine alkyl or cycloalkyl). In an even more preferred embodiment, at least one of L, L ¹ , L ^{1 ′} and L ² is —P (cyclohexyl) ₃ , —P (cyclopentyl) ₃ , —P (isopropyl) ₃ , and —P ( Each selected from the group consisting of phenyl) ₃ . Even more preferably, at least one of L, L ¹ , L ^{1 ′} and L ² is an NHC ligand. In a preferred embodiment, L is NHC, L ¹ is P (cyclohexyl) ₃ or —P (cyclopentyl) ₃ , L ^{1 ′} and L ² are each a heterocyclic ligand, optionally aromatic And those which together form a bidentate ligand. Preferably L ^{1 ′} and L ² are each independently pyridine or a pyridine derivative.

(式中、R、R¹、R'、R''、R⁶、R⁷、R⁸、R⁹、R¹⁰及びR¹¹は、各々独立に水素又はC₁-C₂₀アルキル、C₂-C₂₀アルケニル、C₂-C₂₀アルキニル、アリール、C₁-C₂₀カルボキシレート、C₁-C₂₀アルコキシ、C₂-C₂₀アルケニルオキシ、C₂-C₂₀アルキニルオキシ、アリールオキシ、C₂-C₂₀アルコキシカルボニル、C₁-C₂₀アルキルチオ、C₁-C₂₀アルキルスルホニル、C₁-C₂₀アルキルスルフィニル、及びシリルからなる群より選択される置換基である)
の配位子が挙げられる。必要に応じて、R、R¹、R⁶、R⁷、R⁸、R⁹、R¹⁰及びR¹¹置換基は、ハロゲン、C₁-C₅アルキル、C₁-C₅アルコキシ、及びフェニルから選択される1個以上の基で各々さらに置換されていてもよいC₁-C₁₀アルキル、C₁-C₁₀アルコキシ、及びアリールからなる群より選択される1個以上の基で置換されていてもよい。さらに、この触媒配位子はいずれも、1個以上の官能基をさらに含んでもよい。好適な官能基の例としては、限定されるものではないが、ヒドロキシル、チオール、チオエーテル、ケトン、アルデヒド、エステル、エーテル、アミン、イミン、アミド、ニトロ、カルボン酸、ジスルフィド、カルボナート、イソシアネート、カルボジイミド、カルボアルコキシ、カルバメート、ハロゲン、アルコール、スルホン酸、ホスフィン、イミド、アセタール、ケタール、ボロネート、シアノ、シアノヒドリン、ヒドラジン、エナミン、スルホン、スルフィド、及びスルフェニルが挙げられる。 Examples of NHC ligands include the general formula:

(Wherein R, R ¹ , R ′, R ″, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen or C ₁ -C ₂₀ alkyl, C _2- C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C ₁ -C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ - C ₂₀ alkoxycarbonyl, a C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl, C ₁ -C ₂₀ alkylsulfinyl, and substituents selected from the group consisting of silyl)
Of the ligand. Optionally, R, R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ substituents can be from halogen, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, and phenyl. Substituted with one or more groups selected from the group consisting of C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, and aryl, each optionally further substituted with one or more selected groups Also good. Further, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include, but are not limited to, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, Carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

In a preferred embodiment, R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of halogen, phenyl, or taken together are C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ from the group consisting of alkoxy, aryl, and hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen Forming cycloalkyl or aryl optionally substituted with one or more groups selected from the group consisting of selected functional groups; and R ¹⁰ and R ¹¹ are each independently C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, aryl, and hydroxyl, thiol, thioether, ketone, aldehyde, ester Ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine , C ₁ -C ₁₀ alkyl or aryl optionally substituted with a functional group selected from the group consisting of sulfone, sulfide, and sulfenyl.

(式中、
R¹²、R¹³、及びR¹⁴は各々独立に水素、C₁-C₁₀アルキル、C₁-C₁₀アルコキシ、アリール、又はヒドロキシル、チオール、チオエーテル、ケトン、アルデヒド、エステル、エーテル、アミン、イミン、アミド、ニトロ、カルボン酸、ジスルフィド、カルボナート、イソシアネート、カルボジイミド、カルボアルコキシ、カルバメート、及びハロゲンから選択される官能基である)
のものである。特に好ましい実施形態においては、R¹²、R¹³、及びR¹⁴は水素、メチル、エチル、プロピル、イソプロピル、ヒドロキシル、及びハロゲンからなる群より各々独立に選択される。最も好ましい実施形態においては、R¹²、R¹³、及びR¹⁴は同じであり、各々メチルである。 In a more preferred embodiment, R ⁶ and R ⁷ are both hydrogen or phenyl, or R ⁶ and R ⁷ together form a cycloalkyl group; R ⁸ and R ⁹ are hydrogen and R ¹⁰ And R ¹¹ are each substituted or unsubstituted aryl. Without being bound by theory, the bulkier R ¹⁰ and R ¹¹ groups provide a catalyst with improved characteristics such as temperature stability. In particularly preferred embodiments, R ¹⁰ and R ¹¹ are the same and each is independently of the general formula:

(Where
R ¹² , R ¹³ , and R ¹⁴ are each independently hydrogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, aryl, or hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, (A functional group selected from amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen)
belongs to. In particularly preferred embodiments, R ¹² , R ¹³ , and R ¹⁴ are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, hydroxyl, and halogen. In the most preferred embodiment, R ¹² , R ¹³ , and R ¹⁴ are the same and are each methyl.

In these complexes, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently hydrogen or C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C _1- C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl and C ₁ -C ₂₀ alkylsulfinyl substituent selected from the group consisting of Le. The imidazolidine ligand is also referred to as an imidazolide-2-ylidene ligand.

  Other examples of neutral electron donor ligands include, for example, furan, thiophene, pyrrole, pyridine, bipyridine, picolilymine, γ-pyran, γ-thiopyran, phenanthroline, pyrimidine, bipyrimidine, pyrazine, indole, coumarone, thionaphthene, Carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, dithiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine , Ligands derived from substituted or unsubstituted heteroarenes such as bisimidazole and bisoxazole.

Examples of substituents are, OH, _{halogen, C (O) OR s1,} OC (O) R s4, C (O) R s2, nitro, NH _{2, cyano, SO 3 M y, OSO 3} M y, NR 20 _{SO 3 M y, N = NR} s2, C 1 -C 12 alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkenyl, C ₁₂ - C ₁₁ heterocycloalkyl, C ₂ -C ₁₁ heterocycloalkenyl, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryloxy, C ₅ -C ₉ heteroaryl, C ₅ -C ₉ terrorist aryloxy, C ₇ - C ₁₁ aralkyl, C ₇ -C ₁₁ aralkyloxy, C ₆ -C ₁₀ heteroaralkyl, C ₈ -C ₁₁ aralkenyl, C ₇ -C ₁₀ heteroaralkenyl, monoamino, diamino, sulfonyl, sulfonamido, carbamide, carbamate, sulfohydrazides, carbohydrazide, a carboxymethyl hydroxamic acid residue, and aminocarbonyl amido, wherein, R _s1 is hydrogen, M _y, C ₁ -C ₁₂ alkyl C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ -C ₁₁ aralkyl or C _6- C ₁₀ heteroaralkyl, R _s4 is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₁₆ -C ₁₀ aryl, C ₅ -C ₁₉ heteroaryl, C ₇ -C ₁₁ aralkyl or C ₆ -C ₁₀ heteroaralkyl, R _s2 and R _s20 are hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C _3- C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkenyl, C ₂ -C ₁₁ heterocycloalkyl, C ₁ -C ₁₁ heterocycloalkenyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ -C ₁₁ aralkyl, C ₆ -C ₁₀ heteroaralkyl, C ₈ -C ₁₁ aralkenyl or C ₇ -C ₁₀ heteroaralkenyl, and substituted by one of the above substituents May be alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, aryloxy, heteroaryl, heteroaryloxy, aralkyl, aralkyloxy, heteroaralkyl, aralkenyl and heteroaralkenyl As well as y is 1 and M is a monovalent metal or y is 1/2 and M is a divalent metal.

In the context of the present specification, the term “metal” and the corresponding cation are alkali metals such as Li, Na or K, alkaline earth metals such as Mg, Ca or Sr, or Mn, Fe, Zn or Ag, and their corresponding cations. Lithium, sodium and potassium ions and their salts are preferred. NH ₂ , monoamino, diamino, carbamide, carbamate, carbohydrazide, sulfonamide, sulfohydrazide and aminocarbonylamide are preferably the groups R ₈ C (O) (NH) _p N (R ₉ )-, --C ( O) (NH) _p NR ₈ R ₉ , R ₈ OC (O) (NH) _p N (R ₉ )-, R ₈ R ₄₀ NC (O) (NH) _p N (R ₉ )-,- -OC (O) (NH) _p NR ₈ R ₉ , --N (R ₄₀ ) C (O) (NH) _p NR ₈ R ₉ , R ₈ S (O) ₂ (NH) _p N (R ₉ ) -; --S (O) ₂ (NH) _p NR ₈ R ₉ ; R ₈ R ₄₀ NS (O) ₂ N (R ₉ )-or --NR ₄₀ S (O) ₂ NR ₈ R ₉ ( Wherein R ₈ , R ₉ and R ₄₀ are independently of each other hydrogen, OH, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkenyl, C ₂ -C ₁₁ heterocycloalkyl, C ₂ -C ₁₁ heterocycloalkenyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ -C ₁₆ aralkyl, C ₈ -C ₁₆ aralkenyl, C ₂ -C C ₈ -C ₁₆ aralkenyl with ₆ alkenylene and C ₆ -C ₁₀ aryl, C ₆ -C ₁₅ hetero Aralkyl, C ₆ -C ₁₅ heteroaralkenyl, or di-C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkyl, or R _{8 ′} R _{9 ′} N wherein R _{8 ′} and R _{9 ′} are independently _{hydrogen, OH, SO 3 M y,} OSO 3 M y, C 1 -C 12 alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₆ -C ₁₀ aryl, C ₅ - C ₈ -C ₁₆ aralkenyl with C ₉ heteroaryl, C ₇ -C ₁₁ aralkyl, C ₆ -C ₁₀ heteroaralkyl, C ₂ -C ₆ alkenylene and C ₆ -C ₁₀ aryl, or di-C ₆ -C ₁₀ Aryl-C ₁ -C ₆ alkyl, which are OH, halogen, C (O) OR _s1 , OC (O) R _s4 , C (O) R _s2 , nitro, NH ₂ , cyano, SO ₃ Z _y , OSO ₃ Z _y , NR ₂₀ SO ₃ Z _y , C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkenyl, C ₂ -C ₁₁ heterocycloalkyl, C ₂ -C ₁₁ heterocycloalkenyl, C ₆ -C ₁₀ arylene , C ₆ -C ₁₀ aryloxy, C ₅ -C ₉ heteroaryl, C ₅ -C ₉ heteroaryloxy, C ₇ -C ₁₁ aralkyl, C ₇ -C ₁₁ aralkyloxy, C ₆ -C ₁₀ heteroaralkyl, C ₈ -C ₁₁ aralkenyl, C ₇ -C ₁₀ heteroaralkenyl, monoamino, diamino, sulfonyl, sulfonamide, carbamide, carbamate, sulfohydrazide, carbohydrazide, carbohydroxamic acid residue and aminocarbonylamide (where R _s1 is hydrogen, Z _y, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl Aryl, C ₇ -C ₁₁ aralkyl or C ₆ -C ₁₀ heteroaralkyl, R _s4 is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ Haitai Aryl, C ₇ -C ₁₁ aralkyl or C ₆ -C ₁₀ heteroaralkyl, R _s2 is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkenyl, C ₂ -C ₁₁ heterocycloalkyl, C ₂ -C ₁₁ heterocycloalkenyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ -C ₁₁ aralkyl, C ₆ -C ₁₀ hetero Aralkyl, C ₈ -C ₁₁ aralkenyl or C ₇ -C ₁₀ heteroaralkenyl, and alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, heterocycloalkyl, optionally substituted by one of the above substituents, Heterocycloalkenyl, aryl, aryloxy, heteroaryl, heteroaryloxy, aralkyl, aralkyloxy, heteroaralkyl, aralkenyl and heteroaralkenyl. May be substituted with one or more substituents selected from the group); p is 0 or 1, y is 1, Z is a monovalent metal, or y is 1 / 2, Z is a divalent metal; or in the case of --NR ₈ R ₉ or --NR _{8 '} R _9' or R ₈ R ₄₀ N-- R ₈ and R ₉ or R _{8 '} And R _{9 ′} or R ₈ and R ₄₀ together are tetramethylene, pentamethylene,-(CH ₂ ) ₂ --O-(CH ₂ ) ₂ -,-(CH ₂ ) _2- S - (CH _{2) 2} - or _{- (CH 2) 2 --NR 7} - (CH 2) 2 - a and, R ₇ is H, C ₁ -C ₆ alkyl, C ₇ -C ₁₁ aralkyl, C (O) R _s2 or sulfonyl).

のヘテロアレーンから誘導される。 A sulfonyl substituent is, for example, of the formula R ₁₀ --SO _2- (wherein R ₁₀ is C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C _6- C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ -C ₁₁ aralkyl or C ₆ -C ₁₀ heteroaralkyl, which are OH, halogen, C (O) OR _s1 , OC (O) R _s4 , C (O) R _s2 , nitro, NH ₂ , cyano, SO ₃ Z _y , OSO ₃ Z _y , NR ₂₀ SO ₃ Z _y , C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxy , C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkenyl, C ₂ -C ₁₁ heterocycloalkyl, C ₂ -C ₁₁ heterocycloalkenyl, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryloxy, C ₅ -C ₉ heteroaryl, C ₅ -C ₉ heteroaryloxy, C ₇ -C ₁₁ aralkyl, C ₆ -C ₁₀ heteroaralkyl, C ₈ -C ₁₁ aralkenyl, C ₇ -C ₁₀ heteroaralkenyl, monoamino , Diamino, sulfonyl, Ruhon'amido, carbamide, carbamate, sulfohydrazide, carbohydrazide, carboxymethyl hydroxamic acid residue, and aminocarbonyl amide (wherein, R _s1 is hydrogen, Z _y, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ - C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ -C ₁₁ aralkyl or C ₆ -C ₁₀ heteroaralkyl, R _s4 is hydrogen , C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ - C ₁₁ aralkyl or C ₆ -C ₁₀ heteroaralkyl, R _s2 and R ₂₀ are hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cyclo Alkenyl, C ₂ -C ₁₁ heterocycloalkyl, C ₂ -C ₁₁ heterocycloalkenyl, C ₆ -C ₁₀ aryl, C ₅ -C ₉ heteroaryl, C ₇ -C ₁₁ aralkyl, C ₆ -C ₁₀ heteroaralkyl, C ₈ -C ₁₁ aralkenyl or C ₇ -C ₁₀ heteroaralkenyl, and substituted for the Alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, aryloxy, heteroaryl, heteroaryloxy, aralkyl, heteroaralkyl, aralkenyl and optionally substituted by one of the groups Optionally substituted by one or more substituents selected from the group consisting of: heteroaralkenyl; y is 1, Z is a monovalent metal, or y is 1/2 And Z is a divalent metal). Preferred neutral electron donor ligands are, for example, the groups:

Of heteroarenes.

である。 More preferred compounds are: L ² and L ^{1 ′} , independently of one another, are unsubstituted or C ₁ -C ₁₂ alkyl, C ₂ -C ₁₁ heterocycloalkyl, C ₅ -C ₉ heteroaryl, halogen It is formed when it is pyridyl substituted with one or more substituents selected from the group consisting of: monoamino, diamino and —C (O) H. An example is

It is.

である。 Another preferred group of compounds is ^{one wherein} L ² and L ^{1 ′ taken} together are unsubstituted or selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl and cyano Bipyridyl, phenanthrolinyl, bithiazolyl, bipyrimidinyl or picolilymine substituted by the above substituents, the substituent alkyl and aryl being C ₁ -C ₁₂ alkyl, nitro, monoamino, diamino and nitro- or diamino-substituted Furthermore, it may be substituted with one or more substituents selected from the group consisting of --N = NC ₆ -C ₁₀ aryl. An example is:

It is.

(式中、Rは水素又はC₁-C₂₀アルキル、C₂-C₂₀アルケニル、C₂-C₂₀アルキニル、アリール、C₁-C₂₀カルボキシレート、C₁-C₂₀アルコキシ、C₂-C₂₀アルケニルオキシ、C₂-C₂₀アルキニルオキシ、アリールオキシ、C₂-C₂₀アルコキシカルボニル、C₁-C₂₀アルキルチオ、C₁-C₂₀アルキルスルホニル、C₁-C₂₀アルキルスルフィニル、及びシリルからなる群より選択される置換基からなる群より選択される)
からなる群より選択される。必要に応じて、R基はC₁-C₁₀アルキル、C₁-C₁₀アルコキシ、並びにハロゲン、C₁-C₅アルキル、C₁-C₅アルコキシ、及びフェニルから選択される1個以上の基でさらに置換されていてもよいアリールからなる群より選択される1個以上の基で置換されていてもよい。さらに、このヘテロ環はいずれも、1個以上の官能基をさらに含んでもよい。好適な官能基の例としては、限定されるものではないが、ヒドロキシル、チオール、チオエーテル、ケトン、アルデヒド、エステル、エーテル、アミン、イミン、アミド、ニトロ、カルボン酸、ジスルフィド、カルボナート、イソシアネート、カルボジイミド、カルボアルコキシ、カルバメート、ハロゲン、アルコール、スルホン酸、ホスフィン、イミド、アセタール、ケタール、ボロネート、シアノ、シアノヒドリン、ヒドラジン、エナミン、スルホン、スルフィド、及びスルフェニルが挙げられる。好ましくは、RはC₁-C₂₀アルキル、アリール、エーテル、アミン、ハライド、ニトロ、エステル及びピリジルからなる群より選択される。 Even more preferably, L ² and L ^{1 ′} are each independently

(Wherein, R is hydrogen or C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C ₁ -C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ -C ₂₀ alkoxycarbonyl, C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl, C ₁ -C ₂₀ alkylsulfinyl, and a silyl Selected from the group consisting of substituents selected from the group)
Selected from the group consisting of Optionally, the R group is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, and one or more groups selected from halogen, C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, and phenyl And may be further substituted with one or more groups selected from the group consisting of optionally substituted aryl. Further, any of the heterocycles may further include one or more functional groups. Examples of suitable functional groups include, but are not limited to, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, Carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl. Preferably, R is selected from the group consisting of C ₁ -C ₂₀ alkyl, aryl, ether, amine, halide, nitro, ester and pyridyl.

(式中、sIMES又はIMesH₂は、

である)。 Preferably, complexes 1-4 and 44-48 are used to make preferred embodiments 5-29 and 49-83 of the complexes of the invention:

(Where sIMES or IMesH ₂ is

Is).

Most preferably, L is an NHC ligand, preferably an imidazolidine ligand, and L ² and L ^{1 ′} are pyridine.

(式中、M及びM'はルテニウム及びオスミウムからなる群より独立に選択され、X、X¹、L²、L^1'、R及びR¹は先に定義された通りであり、X'及びX^1'は置換されていても無置換であってもよく、X及びX¹が選択される群から独立に選択され、R'及びR^1'は置換されていても無置換であってもよく、R及びR¹が選択される群から独立に選択され、L^1''はL^1'が選択される群から選択され、L^2'は任意の二座配位性中性電子供与配位子であり、L³は任意の四座配位性電子供与配位子である)
のものであってもよい。 And the complex has the formula:

(Wherein M and M ′ are independently selected from the group consisting of ruthenium and osmium, X, X ¹ , L ² , L ^{1 ′} , R and R ¹ are as defined above, and X ′ and X ^{1 ′} may be substituted or unsubstituted, X and X ¹ are independently selected from the selected group, and R ′ and R ^{1 ′} may be substituted or unsubstituted. Often, R and R ¹ are independently selected from the selected group, L ^{1 ''} is selected from the group of selected L ^{1 '} , and L ^2' is any bidentate neutral electron donor. L ³ is any tetradentate electron donating ligand)
It may be.

(式中、M、L、L¹、L^1'、L²、X、X¹、R及びR¹は上記で定義された通りである)
の触媒である。そのような場合、出発錯体を以下のもの：

から選択することができる。 It is also possible to cumulate the carbene complexes of the invention. For example, one embodiment of the invention is a general structure:

(Wherein M, L, L ¹ , L ^{1 ′} , L ² , X, X ¹ , R and R ¹ are as defined above)
It is a catalyst. In such cases, the starting complex is:

You can choose from.

同様に、化合物6〜29にも、対応する積み重ねられた錯体がある。 Stacked pentacoordination complexes, such as those found in complexes 1-4 (a, b), can be used to produce the stacked hexacoordination complexes of the present invention in the process of the present invention. For example, the stacked complexes corresponding to complex 5 are as follows:

Similarly, compounds 6-29 have corresponding stacked complexes.

In all of the above carbene complexes, at least one of L, L ¹ , L ^{1 ′} , L ² , X, X ¹ , R and R ¹ is the other L, L ¹ , L ^{1 ′} , L ² , X, It may be linked to at least one of X ¹ , R and R ¹ to form a bidentate or multidentate ligand array.

(式中、M、X、X¹、L、L¹、R及びR¹は先に定義された通りであり；第3の中性電子供与配位子は金属中心に結合している)
の先述の五配位金属カルベン触媒錯体とを接触させることにより作製する。スキーム1：

(式中、M、X、X¹、L、L¹、L^1'、L²、R及びR¹は先に定義された通りである)
は、本発明の六配位金属カルベン錯体を形成するための一般的な合成反応を示す。 Synthesis In general, the catalyst of the present invention is combined with an excess of a neutral electron donor ligand such as pyridine and the formula:

(Wherein M, X, X ¹ , L, L ¹ , R and R ¹ are as defined above; the third neutral electron donating ligand is attached to the metal center)
It is prepared by contacting with the above-mentioned pentacoordinate metal carbene catalyst complex. Scheme 1:

(Wherein M, X, X ¹ , L, L ¹ , L ^{1 ′} , L ² , R and R ¹ are as defined above)
These show general synthetic reactions for forming the hexacoordinate metal carbene complexes of the present invention.

に示す。 A preferred embodiment synthesis is illustrated in Scheme 2:

Shown in

As shown by Schemes 1 and 2, in the presence of excess ligand L ^2, pentacoordinated complex loses L ¹ ligand, ligand L ² and L ^{1 'is} bound to the metal center . The ligands L ² and L ^{1 ′} may be the same compound, for example pyridine (when an excess of pyridine is used), or may together form a bidentate ligand. Alternatively, L ¹ and L ^{1 ′} may be the same, but in this case the pentacoordinate compound need not lose the L ¹ ligand in the presence of excess L ² .

(式中、M、X、X¹、L、L¹、L^1'、L²、R及びR¹は先に定義された通りである)
の積み重ねられたカルベン錯体であってもよい。これらの錯体の合成は、出発化合物をそれぞれ五配位ビニリデン又は五配位クムレンにすること以外はスキーム1に従う。ビニリデンの好ましい実施形態の合成は、スキーム3：

に見出すことができる。 The complex of the present invention has the general formula:

(Wherein M, X, X ¹ , L, L ¹ , L ^{1 ′} , L ² , R and R ¹ are as defined above)
The carbene complex may be stacked. The synthesis of these complexes follows Scheme 1 except that the starting compound is pentacoordinate vinylidene or pentacoordinate cumulene, respectively. The synthesis of a preferred embodiment of vinylidene is shown in Scheme 3:

Can be found in

Other preferred compounds synthesized by the method of the present invention include those in which L ² and L ^{1 ′} form a bidentate ligand:

The six-coordinate catalyst complex of the present invention provides synthetic utility and utility in catalytic reactions. Without being bound by theory, these complexes contain labile ligands such as pyridine and chloride ligands and serve as general starting materials for the synthesis of new ruthenium metal carbene complexes. . The chloride ligand is more labile than in the corresponding pentacoordinate phosphine-based complex. As mentioned above, X and X ¹ are any anionic ligand. Preferably, X and X ¹ are selected from the group consisting of chloride, bromide, iodide, Tp, alkoxide, amide, and thiolate. Pyridine ligands are more unstable than phosphines in the corresponding pentacoordinate phosphine-based complexes. Also, as described above, L, L ¹ , L ^{1 ′} , and L ² may be any neutral electron donor ligand such as an NHC ligand. Depending on the size of the ligand, one or more neutral ligands (other than NHC) may bind to the metal center.

に示されるように、六配位錯体は中性電子供与配位子を失って五配位触媒錯体を生成し得る。この反応は過剰のL²の存在下で他の方向に進行して六配位錯体を生成することもできる。 Interestingly, the catalyst complexes of the invention can be used both in metathesis reactions or in the formation of complexes based on NHC ligands. Scheme 4:

As shown, the hexacoordination complex can lose a neutral electron donor ligand to form a pentacoordination catalyst complex. This reaction can also proceed in the other direction in the presence of excess L ² to form a hexacoordination complex.

スキーム5に示されるように、L¹配位子はまた、四配位種に結合して五配位錯体を形成し得る。 The pentacoordination complex can also lose the L ¹ ligand to form a tetracoordinate species with metathesis activity (Scheme 5):

As shown in Scheme 5, the L ¹ ligand can also bind to a tetracoordinate species to form a pentacoordinate complex.

に示されるように、オレフィンの存在下で重合を開始するか、又は保護されたNHC-配位子
の存在下でNHC-配位子に基づく五配位錯体を形成し得る(スキーム7)。

The tetracoordinated species is then scheme 6:

As shown, can initiate polymerization in the presence of olefins or form NHC-ligand based pentacoordination complexes in the presence of protected NHC-ligands (Scheme 7).

は一般的には保護形態のN-ヘテロ環カルベン(NHC)を示す。 The structure NHC-AB:

Generally refers to the protected form of N-heterocyclic carbene (NHC).

などの不飽和種のものであってもよい。 In addition, protected NHC-AB

It may be an unsaturated species.

は、本発明の六配位錯体と共に使用するための保護されたNHC配位子の好ましい実施形態を示す。 In the above structure, A is preferably H, Si, Sn, Li, Na, MgX ³ and acyl, where X ³ is any halogen and B is CCl ₃ ; CH ₂ SO ₂ Ph; C ₆ F ₅ ; OR ²¹ ; and N (R ²² ) (R ²³ ), wherein R ²¹ is Me, C ₂ H ₅ , iC ₃ H ₇ , CH ₂ CMe ₃ , CMe ₃ , C ₆ H ₁₁ (cyclohexyl), CH ₂ Ph, CH ₂ norbornyl, CH ₂ norbornenyl, C ₆ H ₅ , 2,4,6- (CH ₃ ) ₃ C ₆ H ₂ (mesityl), 2,6-i-Pr ₂ C ₆ H ₂ , 4 -Me-C ₆ H ₄ (tolyl), selected from the group consisting of 4-Cl-C ₆ H ₄ ; R ²² and R ²³ are Me, C ₂ H ₅ , iC ₃ H ₇ , CH ₂ CMe ₃ , CMe ₃ , C ₆ H ₁₁ (cyclohexyl), CH ₂ Ph, CH ₂ norbornyl, CH ₂ norbornenyl, C ₆ H ₅ , 2,4,6- (CH ₃ ) ₃ C ₆ H ₂ (mesityl), 2,6- i-Pr ₂ C ₆ H ₂ , 4-Me-C ₆ H ₄ (tolyl), and 4-Cl—C ₆ H ₄ are independently selected. This approach is associated with the thermal generation of NHC ligands from stable (protected) NHC derivatives with a certain amount of AB release. One more preferred method of generating reactive NHC ligands is to use a stable carbene precursor where the AB compound is also a reactive NHC ligand. A detailed description of protected NHC and related methods of synthesis and use can be found in US Patent Application Nos. 10 / 107,531 and 10 / 138,188, the contents of each of which are incorporated herein by reference. Shall be. The following structure for sImesHCCl ₃ :

Shows preferred embodiments of protected NHC ligands for use with the hexacoordination complexes of the present invention.

The pentacoordination complex based on the NHC ligand can then lose the L ligand to form a tetracoordinate species with metathesis activity and initiate the polymerization reaction in the presence of the olefin (Scheme 8):

Hexacoordination complexes can also undergo ligand exchange. The ligand exchange then replaces NHC with another neutral electron donor ligand, resulting in a hexacoordination complex based on the NHC ligand (Scheme 9):

In all of the above schemes and complexes, M, X, X ¹ , L, L ¹ , L ^{1 ′} , L ² , R, R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^y is as defined above.

Reaction of complex 1 with a large excess (~ 100 equivalents) of pyridine causes a rapid color change from red to light green, and the resulting solution is transferred to cold (-10 ° C) pentane to add bis-pyridine. A precipitate of the product (ImesH ₂ ) (Cl) ₂ (C ₅ H ₅ N) ₂ Ru = CHPh (31) is obtained. Complex 31 can be purified by washing several times with pentane and is isolated as an air-stable green solid that is soluble in CH ₂ Cl ₂ , benzene and THF. This procedure yields complex 31 in 80-85% yield and can be easily performed on a multigram scale.

Crystals suitable for X-ray crystal structure determination were grown by vapor diffusion of pentane into 31 saturated benzene solutions at room temperature. The collection and refinement parameters for crystal analysis are summarized in Table 1.

A labeling diagram for complex 31 is shown in FIG. 1 and representative bond lengths and bond angles are reported in Table 2.

Several structural isomers of bis-pyridine adducts are possible, but the solid state structure is that pyridine binds to benzylidene and N-heterocyclic carbene ligands in a cis-structure that occupies a trans coordination site. Is shown. The Ru = C (1) (benzylidene carbon) bond length of 1.873 (4) Å is (Cl) ₂ (PCy ₃ ) ₂ Ru = CHPh [d (Ru = C _α ) = 1. 838 (2) Å] and complex 1 It is slightly longer than that in pentacoordinate ruthenium olefin metathesis catalysts such as [d (Ru = C _α ) = 1.835 (2) Å]. The extended Ru = _Cα bond in 31 appears to arise from the presence of the transpyridine ligand. The Ru-C (38) (N-heterocyclic carbene) bond length of 2.033 (4) Å is about 0.05Å shorter than that in Complex 1, which is a smaller size for pyridine compared to PCy ₃ . It seems to be due to having a moderate transformer effect. The difference of 0.15% in the Ru-C (1) and Ru-C (38) bond distances emphasizes the former covalent nature and the coordinative nature of the latter ruthenium-carbene bond. Interestingly, the two Ru-N bond distances differ by more than 0.15 km, indicating that benzylidene ligands exhibit significantly greater trans effects than N-heterocyclic carbenes.

The mechanism of this ligand substitution was determined by examining the kinetics of the reaction between complex 1 and pyridine. The reaction of complex 1 (0.88 M in toluene) with excess pyridine-d ₅ (0.18-0.69 M) is accompanied by a 150 nm red-shifted visible MLCT absorbance, so this conversion is followed by UV-vis spectroscopy. can do. The disappearance of the starting material (502 nm) was monitored at 20 ° C. and in all cases the data was adapted to the first order reaction rate for 5 half-lives. A plot of k _obs vs. [C5D5N] is presented in FIG. The data shows an excellent linear fit (R ² = 0.999) even at high concentrations of pyridine, and the y-intercept (1.1 x 10 ^-3 ) of this line is very close to zero. When the rate constant (k _B ) of phosphine dissociation in complex 1 was measured independently by a ³¹ P magnetization transfer experiment, k _B was 4.1 × 10 ⁻⁵ s ⁻¹ at 20 ° C. This k _B value places an upper limit on the rate of dissociated ligand exchange at 1, and the observed rate constant for pyridine substitution is clearly three orders of magnitude higher than k _B. Taken together, these results indicate that the substitution of PCy ₃ for pyridine proceeds by a coupled mechanism with a second order rate constant of 5.7x 10 ^-2 M ^-1 s ^-1 at 20 ° C. . In contrast, replacement of one phosphine ligand with an olefin substrate, which is an initiating event in the olefin metathesis reaction, occurs via a dissociation mechanism.

Initiation reactivity studies of complex 31 showed that both pyridine ligands were unstable as substituents. For example, benzylidene 31 reacts immediately with 1.1 equivalents of PCy ₃ to release pyridine and regenerated complex 1. This equilibrium can be reversed in the direction of the pyridine adduct by adding excess C ₅ D ₅ N, but can be easily restored by removing volatiles under reduced pressure.

The easy reaction of 31 with PCy ₃ shows that pyridine can be replaced by other incoming ligands, and the reaction of bis-pyridine complexes with various phosphines has the general formula (ImesH ₂ ) ( It has been found that PR ₃ ) (Cl) ₂ Ru = CHPh provides a simple and different route to the new ruthenium benzylidene. The combination of 31 and 1.1 equivalents of PR ₃ results in a color change from green to red / brown and the formation of the corresponding PR ₃ adduct. Residual pyridine can be removed under reduced pressure and the ruthenium product is purified by several washes with pentane and / or column chromatography. This ligand substitution works well for various alkyl and aryl substituted phosphines such as PPH ₃ , PBn ₃ , and P (n-Bu) ₃ to produce complexes 32, 33, and 34.

In addition, para-substituted triphenylphosphine derivatives 35, 36, and 37 (including para-substituents CF ₃ , Cl, and OMe, respectively) can be produced using the method of the present invention. Since P (p-CF ₃ C ₆ H ₄ ) is an extremely electron-poor phosphine (χ = 20.5 cm ⁻¹ ), the possibility of synthesizing the complex 35 is particularly noteworthy. Triarylphosphine ruthenium complexes 32, 35-37 are useful catalysts because they are nearly two orders of magnitude more active than the original complex 1 for olefin metathesis reactions.

There appears to be steric and electronic limitations on the incoming phosphine ligand in the pyridine substitution reaction. For example, complex 31 does not react with P (o-tolyl) ₃ to produce a stable product, possibly due to the enormous size of the incoming ligand. The cone angle of P (o-tolyl) ₃ is 194 °, whereas that of PCy ₃ (one of the larger phosphines shown to efficiently replace 31 pyridine) is 170 °. Furthermore, the electron-poor phosphine P (C ₆ F ₆ ) ₃ does not show reactivity with 31 even under forced conditions. This ligand has a significantly lower electron donating capacity (χ = 33.6 cm ⁻¹ ) than P (p-CF ₃ C ₆ H ₄ ) ₃ (χ = 20.5 cm ⁻¹ ), and from PCy ₃ Also have a large cone angle (θ = 184 °).

The method described herein represents a dramatic improvement over the conventional synthetic route of the complex (NHC) (PR ₃ ) (Cl) ₂ Ru═CHPh. The initial preparation of these compounds involved the reaction of the bis-phosphine precursor (PR ₃ ) ₂ (Cl) ₂ Ru═CHPh with NHC ligands. These transformations often had low yields (especially when NHC was small) and necessitated parallel synthesis of ruthenium precursors, each containing a PR ₃ ligand. Furthermore, PPh ₃ bis including small, electron-donating low PR ₃ ligands than (θ = 145 °;; χ = 20.5 cm -1 pK a = 2.73) - can not be produced phosphine starting materials Imposes significant limitations on the complexes that are obtainable by earlier production methods.

The 31 chlorine ligands are also substantially unstable compared to those in the original complex 1. For example, 31 reacts quantitatively with NaI within 2 hours at room temperature to give (ImesH ₂ ) (I) ₂ (C ₅ H ₅ N) Ru = CHPh (38). In contrast, the reaction of 1 with NaI takes about 8 hours to reach completion under ideal conditions. Interestingly, ¹ H NMR spectroscopy shows that the diiodide complex 38 contains only one pyridine ligand, but a similar dichloride species 31 coordinates to 2 equivalents of pyridine. Both the relatively large size iodide ligand and the lower electron affinity at the metal center in 38 (compared to 31) are thought to contribute to the formation of pentacoordination complexes in this system.

Complex 31 also reacts quantitatively with KTp [Tp = Tris (pyrazolyl) borate] within 1 hour at 25 ° C. to give the light green product Tp (ImesH ₂ ) (Cl) Ru = CHPh (39) Although similar, the similar reaction between Complex 1 and KTp is extremely slow (the latter only proceeds with less than 50% completeness after several days at room temperature). After removing the solvent under reduced pressure, filtering and washing several times with pentane and methanol gives 39 as an air and humidity stable solid. Preliminary ¹ H NMR studies also showed that the combination of 31 and excess KO ^t -Bu resulted in a tetracoordinate benzylidene, (ImesH ₂ )-(O ^t Bu) ₂ Ru = CHPh (40) within 10 minutes at ambient temperature. It shows that it is generated quantitatively. In contrast, the reaction of 1 to form 40 with KO ^t -Bu does not proceed to completion after several days at 35 ° C. Complex 40 is thought to be a model of (IMesH ₂ ) (Cl) ₂ Ru═CHPh, a 14-electron intermediate involved in the olefin metathesis reaction of 1.

The present invention is for producing (IMesH ₂ ) (Cl) ₂ (C ₅ H ₅ N) ₂ Ru═CHPh (31) from (IMesH ₂ ) (Cl) ₂ (PCy ₃ ) Ru═CHPh (1). A high yield method is provided. In contrast to the reaction of 1 with the olefin substrate, this ligand substitution proceeds by a coupled mechanism. Complex 31 reacts readily with phosphine, providing a way to obtain the new complexes discussed herein. Complex 31 also reacts with KO ^t -Bu, NaI, and KTp to provide novel tetracoordinate, pentacoordinate, and hexacoordinate ruthenium benzylidene. The method of the present invention is useful for facilitating the development of new ruthenium olefin metathesis catalysts comprising structurally different ligand arrays.

Olefin metathesis:
The complexes of the present invention are particularly useful in olefin metathesis reactions for polymerization reactions. These catalysts include, but are not limited to, ring-opening metathesis polymerization of cyclic or non-distorted cyclic olefins, ring-closing metathesis of acyclic dienes, acyclic diene metathesis polymerization (“ADMET”), It can be used in various metathesis reactions such as self-metathesis reaction and cross-metathesis reaction, alkyne polymerization, carbonyl olefination, unsaturated polymer depolymerization, telechelic polymer synthesis, and olefin synthesis.

The most preferred olefin monomer for use in the present invention is substituted or unsubstituted dicyclopentadiene (DCPD). Various DCPD suppliers and purity such as Lyondell 108 (94.6% purity), Veliscol UHP (99 +% purity), BF Goodrich Ultrene® (97% and 99% purity), and Hitachi (99 +% purity) Can be used. Other preferred olefin monomers include trimer, tetramer, pentamer and other cyclopentadiene oligomers; cyclooctadiene (COD; DuPont); cyclooctene (COE, Alfa Aesar); cyclohexenyl norbornene (Shell); norbornene (Aldrich) And norbornene dicarboxylic anhydride (Elf Atochem); and substituted norbornene such as butyl norbornene, hexyl norbornene, octyl norbornene, and decyl norbornene. Preferably, the olefin moiety includes mono- or disubstituted olefins and cycloolefins containing 3 to 200 carbons. Most preferably, the metathesis active olefin moiety includes, for example, cyclopropene, cyclobutene, cycloheptene, cyclooctene, [2,2,1] bicycloheptene, [2,2,2] bicyclooctene, benzocyclobutene, cyclopentene, Examples include cyclopentadiene oligomers such as trimer, tetramer and pentamer, and substituted or unsubstituted cyclic or polycyclic olefins such as cyclohexene. Such compositions also have one or more carbon atoms derived from radical fragments such as halogen, pseudohalogen, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, etc. It is also understood that the skeleton carrying substituents or skeletons in which one or more carbon atoms are replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus, antimony, or boron. For example, olefin is thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, It may be substituted with one or more groups such as halogen or pseudohalogen. Similarly, olefins are C ₁ -C ₂₀ alkyl, aryl, acyl, C ₁ -C ₂₀ alkoxide, aryl oxide, C ₃ -C ₂₀ alkyl diketonate, aryl diketonate, C ₁ -C ₂₀ carboxylate, aryl sulfonate, C ₁ -C ₂₀ alkylsulfonate, C ₁ -C ₂₀ alkylthio, arylthio, C ₁ -C ₂₀ alkylsulfonyl, and C ₁ -C ₂₀ alkylsulfinyl, C ₁ -C ₂₀ alkyl phosphates, aryl phosphates (here, These groups may be substituted with one or more groups such as

Examples of preferred polymerizable norbornene-type monomers include, but are not limited to, norbornene (bicyclo [2.2.1] hept-2-ene), 5-methyl-2-norbornene, ethyl norbornene, propyl norbornene, isopropyl Norbornene, butyl norbornene, isobutyl norbornene, pentyl norbornene, hexyl norbornene, heptyl norbornene, octyl norbornene, decyl norbornene, dodecyl norbornene, octadecyl norbornene, p-tolyl norbornene, methylidene norbornene, phenyl norbornene, ethylidene norbornene, vinyl norbornene Cyclopentadiene, endo-dicyclopentadiene, tetracyclododecene, methyltetracyclododecene, tetracyclododecadiene, dimethyltetra Lacyclododecene, ethyltetracyclododecene, ethylidenyltetracyclododecene, phenyltetracyclodecene, symmetric and asymmetric trimers and tetramers of cyclopentadiene, 5,6-dimethylnorbornene, propenylnorbornene, 5,8-methylene-5a, 8a -Dihydrofluorene, dicyclohexenyl norbornene, dimethanohexahydronaphthalene, endo, exo-5,6-dimethoxynorbornene, endo, endo-5,6-dimethoxynorbornene, 2,3-dimethoxynorbornadiene, 5,6-bis ( Chloromethyl) bicyclo [2.2.1] hept-2-ene, 5-tris (ethoxy) silylnorbornene, 2-dimethylsilylbicyclo [2.2.1] hepta-2,5-diene, 2,3-bistrifluoromethylbicyclo [2.2.1] Hepta-2,5-diene, 5-fluoro-5-pentafluoroethyl-6-, 6-bis (trifluoromethyl ) Bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5-heptafluoroisopropyl-6-trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 2,3,3, 4,4,5,5,6-octafluorotricyclo [5.2.1.O] dec-8-ene, and 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5,6-dimethyl -2-norbornene, 5-a-naphthyl-2-norbornene, 5,5-dimethyl-2-norbornene, 1,4,4a, 9,9a, 10-hexahydro-9,10 [1 ', 2']- Benzeno-1,4-
Methanoanthracene, indanylnorbornene (i.e., reaction product of 1,4,4,9-tetrahydro-1,4-methanofluorene, CPD and indene), 6,7,10,10-tetrahydro-7,10-methano Fluoranthene (ie, the reaction product of CPD and acenaphthalene), 1,4,4,9,9,10-hexahydro-9,10 [1 ', 2']-benzeno-1,4-methanoanthracene, Endo, endo-5,6-dimethyl-2-norbornene, endo, exo-5,6-dimethyl-2-norbornene, exo, exo-5,6-dimethyl-2-norbornene, 1,4,4,5, 6,9,10,13,14,14-decahydro-1,4-methanobenzocyclododecene (i.e., the reaction product of CPD and 1,5,9-cyclododecatriene), 2,3,3,4 , 7,7-Hexahydro-4,7-methano-1H-indene (i.e., the reaction product of CPD and cyclopentene), 1,4,4,5,6,7,8,8-octahydro-1,4- Methanonaphthalene (i.e., the reaction product of CPD and cyclohexene) ), 1,4,4,5,6,7,8,9,10,10-decahydro-1,4-methanobenzocyclooctene (i.e., the reaction product of CPD and cyclooctene), and 1,2, 3,3,3,4,7,7,8,8-decahydro-4,7-methanocyclopenta [a] indene.

  These olefin monomers can be used alone or mixed together in various combinations to adjust the properties of the olefin monomer composition. For example, a mixture of cyclopentadiene dimer and trimer results in a cured olefin copolymer that results in a lower melting point and increased mechanical strength and stiffness compared to pure poly-DCPD. As another example, the incorporation of COD, norbornene, or alkyl norbornene copolymers tends to result in relatively soft and elastic cured olefin copolymers. The resulting polyolefin composition formed from the metathesis reaction is easy to set temperature, and is not limited to additives, stabilizers, speed modifiers, hardness and / or toughness modifiers, fillers, and the like. Carbon, glass, aramid (e.g. Kevlar® and Twaron®), polyethylene (e.g. Spectra® and Dyneema®), polyparaphenylene benzobisoxazole (e.g. Zylon (e.g. Registered trademark)), polybenzamidazole (PBI), and hybrids thereof and other polymer fibers.

The metathesis reaction may contain a forming aid as necessary. Known adjuvants include antistatic agents, antioxidants (primary antioxidants, secondary antioxidants, or mixtures thereof), ceramics, light stabilizers, plasticizers, dyes, pigments, fillers, Reinforcing fibers, lubricants, adhesion promoters, viscosity increasing agents, and demolding enhancing agents can be mentioned. Examples of fillers for improving photophysical, mechanical and electrical properties include glass and quartz in the form of powders, beads and fibers, metal and metalloid oxides, carbonates (e.g. MgCO ₃ , CaCO ₃ ), dolomite, metal sulfates (eg, gypsum and barite), natural and synthetic silicates (eg, zeolite, wollastonite, and feldspar), carbon fibers, and plastic fibers or powders.

  UV and oxidation resistance of polyolefin compositions obtained from metathesis reactions using carbene complexes of the present invention is described in U.S. Patent Application No. 09 / 498,120 filed February 4, 2000, the contents of which are hereby incorporated by reference. Primary antioxidants (e.g., sterically hindered phenols), secondary antioxidants (e.g., organophosphites, thioethers, etc.), light stable Enhanced by the addition of various stabilizing additives such as oxidants (e.g. hindered amine light stabilizers or HALS) and UV light absorbers (e.g. hydroxybenzophenone absorbers, hydroxyphenylbenzotriazole absorbers, etc.) can do.

  Examples of primary antioxidants include, for example, 4,4′-methylenebis (2,6-di-tert-butylphenol) (Ethanox 702®; Albemarle Corporation), 1,3,5-trimethyl-2, 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Ethanox 330®; Albermarle Corporation), octadecyl-3- (3 ′, 5′-di-tert-butyl -4'-hydroxyphenyl) propionate (Irganox 1076®; Ciba-Geigy), and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox® Trademark) 1010; Ciba-Geigy). Examples of secondary antioxidants include tris (2,4-di-tert-butylphenyl) phosphite (Irgafos® 168; Ciba-Geigy), 1:11 (3,6,9- Xadecyl) bis (dodecylthio) propionate (Wingstay (registered trademark) SN-1; Goodyear). Examples of light stabilizers and absorbers include bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxy Phenyl] methyl] butyl malonate (Tinuvin® 144 HALS; Ciba-Geigy), 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (Tinuvin®) 328 absorbent; Ciba-Geigy), 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenyl (Tinuvin® 327 absorbent; Ciba-Geigy), 2- And hydroxy-4- (octyloxy) benzophenone (Chimassorb® 81 absorbent; Ciba-Geigy).

  Further, triphenylphosphine (TPP), tricyclopentylphosphine, as described in U.S. Patent No. 5,939,504 and U.S. Patent Application No. 09 / 130,586, the contents of each of which are incorporated herein by reference, Add a suitable rate modifier to the olefin monomer, such as tricyclohexylphosphine, triisopropylphosphine, trialkyl phosphite, triaryl phosphite, mixed phosphite, or other Lewis bases to retard polymerization rate as needed Or it can be accelerated.

  The resulting polyolefin composition, and a part or product of a product produced therefrom, for example, Reaction Injection Molding (RIM), Resin Transfer Molding (RTM) and VARTM (vacuum assisted RTM) and SCRIMP (Seemann Composite Resin Infusion Molding) Process), etc., can be processed by various methods such as vacuum casting, open casting, rotational molding, centrifugal casting, filament winding, and mechanical processing. These processing compositions are known in the art. Various molding and processing techniques are described in, for example, PCT Publication WO 97/20865, and US patents entitled `` Polymer Processing Methods and Techniques Using Pentacoordinated or Hexacoordinated Ruthenium or Osmium Methathesis Catalysts '' filed on March 1, 2002. Provisional application 60 / 360,755, the disclosure of which is hereby incorporated by reference.

  The metathesis reaction can occur in the presence or absence of a solvent. Examples of solvents that can be used in the polymerization reaction include organic, protic, or aqueous solvents that are preferably inert under the polymerization conditions. Examples of such solvents include aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Preferred solvents include benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water or mixtures thereof. More preferably, the solvent is benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, or a mixture thereof. Most preferably, the solvent is toluene or a mixture of benzene and methylene chloride. The solubility of the polymer formed in the polymerization reaction will depend on the choice of solvent and the molecular weight of the resulting polymer.

  The complexes of the invention have a well-defined ligand environment that allows flexible modification and good tuning of activity levels, stability, solubility and ease of recovery of these catalysts. The solubility of the carbene compound can be controlled by appropriate selection of hydrophobic or hydrophilic ligands, which are known in the art. The desired solubility of the catalyst will be determined primarily by the solubility of the reaction substrate and reaction product.

The metal carbene complexes of the present invention exhibited high onset rates that allowed most (if not all) of the complexes added to the reaction to be consumed. Therefore, a small amount of catalyst is wasted in the metathesis reaction. In contrast, previous pentacoordinate initiators have a higher amount of extractables (ie, unpolymerized monomers) remaining after the reaction is complete. The propogation rate is also delayed by the presence of two pyridine ligands. The high initiation rate and low propagation rate result in a polymer with narrow polydispersity compared to that achieved using the initial pentacoordination complex. It was further determined that heat increases the onset rate. Thermal initiation of pentacoordinate complexes can be found in US Pat. No. 6,107,420, the contents of which are hereby incorporated by reference. In general, the initiation and / or rate of metathesis polymerization using the catalyst of the present invention is controlled by a process comprising contacting the catalyst of the present invention with an olefin and heating the reaction mixture. In result of surprising and was not expected, T _max Thermal initiation of the catalyst of the present invention is significantly higher than the T _max about previous pentacoordinated catalysts. Without being bound by theory, this is the case in a type of system filled with the part or product being manufactured (e.g. a system containing reinforcing fillers, fibers, beads, etc.) in a reaction using a metathesis catalyst. In some cases, the filling material is important in acting as a heat absorption source. When previous pentacoordinate catalysts were used, post-cure treatment was sometimes required due to the effect of the heat absorption source produced by the filling system. ROMP polymerization in the presence of a peroxide crosslinker using a pentacoordinate catalyst is discussed in US Pat. No. 5,728,785, the contents of which are hereby incorporated by reference. In contrast, reactions using the hexacoordination catalyst of the present invention produce significantly higher internal heat. This high T _max reduces the need for post cure treatment. Furthermore, even when peroxides or radicals are added to promote crosslinking, the degree of crosslinking in the portion using the radical mechanism is increased compared to the portion produced using the previous pentacoordinated metathesis catalyst. Furthermore, its half-life depends on the maximum temperature. With the catalysts of the present invention, the half-life is substantially reduced, thus requiring less catalyst and providing significant commercial benefits. Without being bound by theory, a higher T _max indicates that more rings are opened and a higher degree of cure exists in the ROMP reaction. With higher T _max , extractables are almost zero, indicating that almost all molecules that can react will react. For example, vinylidene is advantageous in that it is more stable at higher temperatures than alkylidene. Saturated Imes ligands as described in protected NHCs (e.g., U.S. Provisional Patent Application Nos. 60 / 288,680 and 60 / 278,311 each of which is incorporated herein by reference) ) Is added to the reaction mixture, a dramatic increase in peak exotherm is observed. Furthermore, the time to reach the peak is significantly reduced. A high peak exotherm means more catalyst is available for polymerization, indicating that extractables are near zero. Furthermore, the catalyst of the present invention has better conversion and better properties even in the presence of fillers and additives.

  For purposes of clarity, specific details of the invention will be described with reference to particularly preferred embodiments. However, it should be understood that these embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the invention.

General Procedures Organometallic compound manipulations were performed using standard Schlenk techniques under an atmosphere of dry argon or in a nitrogen-filled vacuum atmosphere drying box (O ₂ <2 ppm). NMR spectra were recorded on a Varian Inova (499.85 MHz for ¹ H; 202.34 MHz for ³¹ P; 125.69 MHz for ¹³ C) or Varian Mercury 300 (299.817 for ¹ H; 121.39 MHz for ³¹ P; 74.45 MHz for ¹³ C) did. ³¹ P NMR spectra were referenced using H ₃ PO ₄ (δ = 0 ppm) as an external standard. UV-vis spectra were recorded on an HP 8452A diode array spectrophotometer.

Materials and Methods Pentane, toluene, benzene, and benzene-d ₆ were dried by passing through a solvent purification column. Pyridine was dried by vacuum transfer from CaH _2. All phosphines as well as KTp were obtained from commercial sources and used as received. Ruthenium complexes 1-4 and 44-48 were prepared according to literature procedures.

(IMesH ₂ ) (C ₁₂ H ₈ N ₂ ) (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) is dissolved in toluene (10 mL) and 1,10-phenanthroline (0.85 grams, 2 molar equivalents) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to brown-orange was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a brown-orange solid precipitated. The precipitate was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₂ H ₈ N ₂ ) as a brown-orange powder (1.7 grams, 96% yield) (Cl) ₂ Ru = CHPh (5) was obtained.

(IMesH ₂ ) (C ₅ H ₄ BrN) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 3-bromopyridine (1.50 grams, 4 molar equivalents) was dissolved. Added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to light green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a light green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₅ H ₄ BrN) ₂ ( Cl) ₂ Ru = CHPh (6) was obtained.

(IMesH ₂ ) (C ₉ H ₁₂ N ₂ ) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL) and 4-pyrrolidinopyridine (1.40 grams, 4 molar equivalents) ) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to light green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a light green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₉ H ₁₂ N ₂ ) ₂ as a light green powder (1.9 grams, 93% yield). (Cl) ₂ Ru = CHPh (7) was obtained.

¹ H NMR (300 MHz, CD ₂ Cl ₂ ): d 19.05 (s, 1H, CHPh), 8.31 (d, 2H, pyridine CH, J _HH = 6.6 Hz), 7.63 (d, 2H, ortho CH, J _HH = 8.4 Hz), 7.49 (t, 1H, Para CH, J _HH = 7.4 Hz), 7.33 (d, 2H, Pyridine CH, J _HH = 6.9 Hz), 7.10 (t, 2H, Meta CH, J _HH = 8.0 Hz), 7.03 (br.s, 2H, Mes CH), 6.78 (br.s, 2H, Mes CH), 6.36 (d, 2H, pyridine CH, J _HH = 6.3 Hz), 6.05 (d, 2H, pyridine CH, J _HH = 6.9 Hz), 4.08 (br.d, 4H, NC H ₂ C H ₂ N), 3.30 (m, 4H, pyrrolidine CH ₂ ), 3.19 (m, 4H, pyrrolidine CH ₂ ), 2.61- 2.22 (multi-peak, 18H, Mes CH ₃ ), 2.02 (m, 4H, pyrrolidine CH ₂ ), 1.94 (m, 4H, pyrrolidine CH ₂ ).

Example: A 75 gram mass of DCPD (containing about 24% trimerized DCPD) at a starting temperature of about 24.2 ° C. with a DCPD: Ru ratio of (about 30,000: 1) (IMesH ₂ ) (C ₉ H ₁₂ Polymerization was carried out using N ₂ ) ₂ (Cl) ₂ Ru = CHPh = 0.151 g.

Result: Time to reach maximum temperature (T _max ) = 194 seconds. T _max = 208.9 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 165 ° C. Residual monomer ratio (toluene extraction at room temperature) = 1.23%.

(IMesH ₂ ) (C ₆ H ₇ N) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 4-methylpyridine (0.88 grams, 4 molar equivalents) was dissolved. Added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to light green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a light green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₆ H ₇ N) ₂ (light green powder (1.5 grams, 84% yield). Cl) ₂ Ru = CHPh (8) was obtained.

(IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL) and 4,4′-bipyridine (0.74 grams, 2 moles) Equivalent) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to brown-orange was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a brown-orange solid precipitated. The precipitate was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) as a brown-orange powder (1.4 grams, 71% yield) ₂ (Cl) ₂ Ru = CHPh (9) was obtained.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ19.15 (s, 1H, CHPh), 8.73-8.68 (multiple peak, 8H, pyridine CH), 7.63-6.77 (multiple peak, 17H, pyridine CH, para CH, meta CH, Mes CH), 4.08 ( br. d, 4H, NC H 2 C H 2 N), 2.61-2.24 ( multi peak, 18H, Mes CH _3).

Polymerization Example: 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 24.2 ° C. (IMesH ₂ ) (C ₁₀ H Polymerization was performed using ₈ N ₂ ) ₂ (Cl) ₂ Ru = CHPh = 0.0153 grams. Result: Time to reach maximum temperature (T _max ) = 953 seconds. T _max = 124.2 ° C.

(IMesH ₂ ) (C ₇ H ₁₀ N ₂ ) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL) and 4-dimethylaminopyridine (1.18 grams, 4 molar equivalents) ) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to light green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a light green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₇ H ₁₀ N ₂ ) ₂ as a light green powder (1.9 grams, 99% yield). (Cl) ₂ Ru = CHPh (10) was obtained.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ19.10 (s, 1H, CHPh), 8.18 (d, 2H, pyridine CH, J _HH = 6.5 Hz), 7.64 (d, 2H, ortho CH, J _HH = 7.5 Hz), 7.48 (t, 1H, Para CH, J _HH = 7.0 Hz), 7.38 (d, 2H, Pyridine CH, J _HH = 6.5 Hz), 7.08 (t, 2H, Meta CH, J _HH = 7.5 Hz), 7.00 (br.s, 2H, Mes CH), 6.77 (br.s, 2H, Mes CH), 6.49 (d, 2H, pyridine CH, J _HH = 6.0 Hz), 6.15 (d, 2H, Pyridine CH, J _HH = 7.0 Hz), 4.07 (br.d, 4H, NC H ₂ C H ₂ N), 2.98 (s, 6H, pyridine CH ₃ ), 2.88 (s, 6H, pyridine CH ₃ ), 2.61 -2.21 (multiple peaks, 18H, Mes CH ₃ ).

Polymerization Example: 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 24.2 ° C. (IMesH ₂ ) (C ₇ H) with a DCPD: Ru ratio of (about 30,000: 1) Polymerization was performed using ₁₀ N ₂ ) ₂ (Cl) ₂ Ru = CHPh = 0.0141 grams. Result: Time to reach maximum temperature (T _max ) = 389 seconds. T _max = 175.3 ° C.

(IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL) and 2,2′-bipyridine (0.74 grams, 2 molar equivalents) ) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to brown-red was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a brown-red solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) as a brown-red powder (0.7 g, 41% yield) (Cl) ₂ Ru = CHPh (11) was obtained.

(IMesH ₂ ) (C ₆ H ₅ NO) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL) and 2-pyridinecarboxaldehyde (1.01 grams, 4 molar equivalents) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to dark blue was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a dark blue solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₆ H ₅ NO) ₂ (as a dark blue powder (1.3 grams, 70% yield). Cl) ₂ Ru = CHPh (12) was obtained.

(IMesH ₂ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 4-phenylpyridine (1.50 grams, 4 molar equivalents) was dissolved. Added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to dark green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a dark green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₁ H ₉ N) ₂ (as a dark green powder (2.0 grams, 97% yield). Cl) ₂ Ru = CHPh (13) was obtained.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ19.23 (s, 1H, CHPh), 8.74 (br.s, 2H, pyridine), 7.91 (br.s, 2H, pyridine), 7.70-7.08 ( Multi-peak, 19H, ortho-CH, para-CH, meta-CH, pyridine), 6.93 (br. S, 2H, Mes CH) 6.79 (br. S, 2H, Mes CH), 4.05 (br. S, 4H, NC H ₂ C H ₂ N), 2.62-2.29 (multiple peaks, 18H, Mes CH ₃ ).

Polymerization Example: 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 13.4 ° C. with a DCPD: Ru ratio of (about 30,000: 1) (IMesH ₂ ) (C ₁₁ H Polymerization was performed using ₉ N) ₂ (Cl) ₂ Ru = CHPh = 0.0153 grams. Result: Time to reach maximum temperature (T _max ) = 145 seconds. T _max = 202.2 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 168 ° C. Residual monomer ratio (toluene extraction at room temperature) = 1.17%.

(IMesH ₂ ) (C ₁₈ H ₁₂ N ₂ ) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL) and 2,2'-biquinoline (1.21 grams, 2 moles) Equivalent) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a slight color change from dark purple to brown-purple was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a brown-purple solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₈ H ₁₂ N ₂ ) as a brown-purple powder (1.8 grams, 93% yield) ₂ (Cl) ₂ Ru = CHPh (14) was obtained.

(IMesH ₂ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru = CHPh Synthesis Complex 1 (1.1 grams, 1.3 mmol) was dissolved in toluene (10 mL), and pyridine (10 mL) was added. The reaction was stirred for 10 minutes during which a color change from pink to light green was observed. The reaction mixture was cannulated into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₅ H ₅ N) ₂ (Cl) as a green powder (0.75 g, 80% yield) ₂ Ru = CHPh was obtained. Samples for elemental analysis were prepared by recrystallization from C ₆ H ₆ / pentane and then drying under reduced pressure. These samples are analyzed as monopyridine adduct (IMesH ₂ ) (C ₅ H ₅ N) (Cl) ₂ Ru═CHPh, possibly due to loss of pyridine under reduced pressure.

¹ H NMR (C ₆ H ₆ ): δ19.67 (s, 1H, CHPh), 8.84 (br.S, 2H, pyridine), 8.39 (br.s, 2H, pyridine), 8.07 (d, 2H, ortho CH, J _HH = 8 Hz), 7.15 (t, 1H, para CH, J _HH = 7 Hz), 6.83-6.04 (br multi-peak, 9H, pyridine, and Mes CH), 3.37 (br d, 4H, C H ₂ C H ₂ ), 2.79 (br s, 6H, Mes CH ₃ ), 2.45 (br s, 6H, Mes CH ₃ ), 2.04 (br s, 6H, Mes CH ₃ ). ¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ314.90 (m, Ru = C HPh), 219.10 (s, Ru- C (N) ₂ ), 152.94, 150.84, 139.92, 138.38, 136.87, 135.99 , 134.97, 131.10, 130.11, 129.88, 128.69, 123.38, 51.98, 51.37, 21.39, 20.96, 19.32. Calculated analysis for C ₃₃ H ₃₇ N ₃ Cl ₂ Ru: C, 61.20; H, 5.76; N, 6.49. Found: C, 61.25; H, 5.76; N, 6.58.

Polymerization Example: 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 12.1 ° C. with a DCPD: Ru ratio of (about 30,000: 1) (IMesH ₂ ) (C ₅ H Polymerization was carried out using ₅ N) ₂ (Cl) ₂ Ru = CHPh = 0.127 gram. Result: Time to reach maximum temperature (T _max ) = 173 seconds. T _max = 201.9 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 164 ° C. Residual monomer ratio (toluene extraction at room temperature) = 1.05%.

Polymerization example: 50 grams of hexyl norbornene at a starting temperature of about 12.2 ° C. with an H _x N: Ru ratio of (about 30,000: 1) (IMesH ₂ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru Polymerized using = CHPh = 0.068 grams. Result: Time to reach maximum temperature (T _max ) = 99 seconds. T _max = 140.7 ° C.

(PCp ₃ ) (C ₁₂ H ₈ N ₂ ) (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂ Synthesis Complex 2 (2.0 grams) was dissolved in toluene (10 mL), and 1,10- Phenanthroline (1.01 grams, 2 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to red-brown was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a red-brown solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCp ₃ ) (C ₁₂ H ₈ N ₂ ) as a red-brown powder (1.8 grams, 98% yield) (Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ (15) was obtained.

(PCp ₃ ) (C ₅ H ₄ BrN) ₂ (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂ Synthesis Complex 2 (2.0 g) was dissolved in toluene (10 mL) and 3-bromopyridine was dissolved. (1.76 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (PCp ₃ ) (C ₅ H ₄ BrN) ₂ (Cl as a green powder (0.2 g, 10% yield). ₂ Ru = CH—CH═C (CH ₃ ) ₂ (16) was obtained.

_{(PCp 3) (C 5 H} 5 N) 2 (Cl) 2 Ru = CH-CH = C (CH 3) 2 Synthesis Complex 2 (2.0 grams) was dissolved in toluene (10 mL), pyridine (0.88 g 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCp ₃ ) (C ₅ H ₅ N) ₂ (Cl ₂ Ru = CH—CH═C (CH ₃ ) ₂ (17) was obtained.

_{(PCp 3) (C 6 H} 7 N) 2 (Cl) 2 Ru = CH-CH = C (CH 3) 2 Synthesis Complex 2 (2.0 grams) was dissolved in toluene (10 mL), 4-methylpyridine (1.04 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to light green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a light green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCp ₃ ) (C ₆ H ₇ N) ₂ (light green powder (1.4 g, 75% yield). Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ (18) was obtained.

(PCy ₃ ) (C ₁₂ H ₈ N ₂ ) (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂ Synthesis Complex 3 (2.0 g) was dissolved in toluene (10 mL), and 1,10- Phenanthroline (0.91 grams, 2 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to orange-brown was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and an orange-brown solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₂ H ₈ N ₂ ) as an orange-brown powder (1.7 grams, 97% yield) (Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ (19) was obtained.

(PCy ₃ ) (C ₅ H ₄ BrN) ₂ (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂ Synthesis Complex 3 (2.0 g) was dissolved in toluene (10 mL) and 3-bromopyridine (1.58 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which no dramatic color change from dark purple was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a purple solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₅ H ₄ BrN) ₂ (Cl ₂ Ru = CH—CH═C (CH ₃ ) ₂ (20) was obtained.

(PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂ Synthesis Complex 3 (2.0 g) was dissolved in toluene (10 mL) and 4-phenylpyridine was dissolved. (1.55 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to brown was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a brown solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl ₂ Ru = CH—CH═C (CH ₃ ) ₂ (21) was obtained.

_{(PCy 3) (C 6 H} 7 N) 2 (Cl) 2 Ru = CH-CH = C (CH 3) 2 Synthesis Complex 3 (2.0 grams) was dissolved in toluene (10 mL), 4-methylpyridine (0.93 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₆ H ₇ N) ₂ (Cl ₂ Ru = CH—CH═C (CH ₃ ) ₂ (22) was obtained.

_{(PCy 3) (C 5 H} 5 N) 2 (Cl) 2 Ru = CH-CH = C (CH 3) 2 Synthesis Complex 3 (2.0 grams) was dissolved in toluene (10 mL), pyridine (0.79 g 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from dark purple to light green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a light green solid precipitated. The precipitate was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₅ H ₅ N) ₂ (light green powder (1.4 g, 83% yield). Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ (23) was obtained.

Polymerization example: 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 52.2 ° C. with a DCPD: Ru ratio of (about 15,000: 1) (PCy ₃ ) (C ₅ H Polymerization was performed using ₅ N) ₂ (Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ = 0.0237 grams. Result: Time to reach maximum temperature (T _max ) = 1166 seconds. T _max = 60.2 ° C.

Polymerization example: 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 49.4 ° C. in the presence of sImesHCCl ₃ = 0.0297 grams (about 15,000: 1: 2) of DCPD Polymerization was performed using (PCy ₃ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ = 0.0237 grams at a: Ru: HCCl ₃ ratio. Result: Time to reach maximum temperature (T _max ) = 715 seconds. T _max = 173.3 ° C.

(IMesH ₂₎ the _{(C 11 H 9 N) 2} (Cl) 2 Ru = CH-CH = C (CH 3) 2 Synthesis Complex 4 (1.5 grams) was dissolved in toluene (10 mL), 4-phenylpyridine (1.13 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 2 hours, during which time a color change from brown to green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₁ H ₉ N) ₂ (Cl ₂ Ru = CH—CH═C (CH ₃ ) ₂ (24) was obtained.

(IMesH ₂ ) (C ₉ H ₁₂ N ₂ ) ₂ (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂ Synthesis Complex 4 (1.5 g) was dissolved in toluene (10 mL) and 4-pyrrolidone was dissolved. Dinopyridine (1.08 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 2 hours, during which time a color change from brown to green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₉ H ₁₂ N ₂ ) ₂ (as a green powder (1.0 gram, 65% yield). Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ (25) was obtained.

¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ19.05 (d, 1H, C H -CH = C (CH ₃ ) ₂ , J _HH = 11 Hz), 8.14 (br.s, 2H, pyridine CH ), 7.69 (d, 1H, CH-C H = C (CH ₃ ) ₂ , J _HH = 11 Hz), 7.36 (d, 2H, pyridine CH, J _HH = 6.0 Hz), 7.04 (s, 2H, Mes CH), 6.81 (s, 2H, Mes CH), 6.36 (br.s, 2H, pyridine CH), 6.12 (d, 2H, pyridine CH, J _HH = 6.0 Hz), 4.06 (m.d, 4H, NC H ₂ C H ₂ N), 3.29 (br. S, 4H, pyrrolidine CH ₂ ), 3.23 (br. S, 4H, pyrrolidine CH ₂ ), 2.55-2.12 (multi-peak, 18H, Mes CH ₃ ), 2.02 ( br, s, 4H, pyrrolidine CH ₂ ), 1.97 (br. s, 4H, pyrrolidine CH ₂ ), 1.10 (s, 3H, CH-CH = C (C H ₃ ) ₂ ), 1.08 (s, 3H, CH -CH = C (C H ₃ ) ₂ ).

Polymerization Example: 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 24.7 ° C. with a DCPD: Ru ratio of (about 30,000: 1) (IMesH ₂ ) (C ₉ H Polymerization was carried out using ₁₂ N ₂ ) ₂ (Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ = 0.0147 grams. Result: Time to reach maximum temperature (T _max ) = 181 seconds. T _max = 200.9 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 144 ° C. Residual monomer ratio (toluene extraction at room temperature) = 3.93%.

(IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru = CH— CH═C (CH ₃ ) ₂ Synthesis Complex 4 (1.5 g) was dissolved in toluene (10 mL), and 4,4 '-Bipyridine (0.57 grams, 2 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 2 hours, during which no dramatic color change from brown was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a brown solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ (as a brown powder (1.0 gram, 64% yield). Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ (26) was obtained.

(IMesH ₂₎ a _{(C 7 H 10 N 2)} 2 (Cl) 2 Ru = CH-CH = C (CH 3) 2 Synthesis Complex 4 (1.5 grams) was dissolved in toluene (10 mL), 4-dimethyl Aminopyridine (0.89 grams, 4 molar equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 2 hours, during which time a color change from brown to green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₇ H ₁₀ N ₂ ) ₂ (as a green powder (0.9 grams, 63% yield). Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ (27) was obtained.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ19.10 (d, 1H, C H -CH = C (CH ₃ ) ₂ , J _HH = 11.5 Hz,), 8.18 (br.s, 2H, pyridine CH), 7.69 (d, 1H, CH-C H = C (CH ₃ ) ₂ , J _HH = 11.5 Hz), 7.41 (br.s, 2H, Mes CH), 6.49 (br.s, 2H, pyridine CH ), 6.24 (br.s, 2H, Mes CH), 4.06 (br.m, 4H, NC H ₂ C H ₂ N), 2.99 (s, 6H, pyridine CH ₃ ), 2.59 (s, 6H, pyridine CH ₃ ), 2.36-2.12 (multiple peak, 18H, Mes CH ₃ ), 1.07 (s, 3H, CH-CH = C (C H ₃ ) ₂ ), 1.06 (s, 3H, CH-CH = C (C H ₃ ) ₂ ).

Polymerization Example: 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 24.2 ° C. (IMesH ₂ ) (C ₇ H) with a DCPD: Ru ratio of (about 30,000: 1) Polymerization was performed using ₁₀ N ₂ ) ₂ (Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ = 0.0138 grams. Result: Time to reach maximum temperature (T _max ) = 200 seconds. T _max = 200.9 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 145 ° C. Residual monomer ratio (toluene extraction at room temperature) = 4.57%.

Polymerization example: 50 grams of hexyl norbornene (IMesH ₂ ) (C ₇ H ₁₀ N ₂ ) ₂ (Cl) ₂ Ru at a starting temperature of about 16.2 ° C. with a DCPD: Ru ratio of (about 30,000: 1) Polymerization was carried out using = CH-CH = C (CH ₃ ) ₂ = 0.0074 grams. Result: Time to reach maximum temperature (T _max ) = 182 seconds. T _max = 141.7 ° C.

(IMesH ₂ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂ Synthesis Complex 4 (1.5 g) was dissolved in toluene (10 mL) and pyridine (10 mL ) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours, during which time a color change from brown to brown-green was observed. The reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₅ H ₅ N) ₂ (Cl ₂ Ru = CH—CH═C (CH ₃ ) ₂ (28) was obtained.

¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ 19.19 (d, 1H, Ru = C H -CH = C (CH ₃ ) ₂ , J _HH = 10.8 Hz), 8.60-6.85 (multiple peaks, 15H, Pyridine, Mes CH, Ru = CH-C H = C (CH ₃ ) ₂ , 4.07 (m, 4H, NC H ₂ C H ₂ N), 2.58-2.27 (multiple peak, 12H, Mes CH ₃ ), 2.31 (s, 3H, Mes CH ₃ ), 2.19 (s, 3H, Mes CH ₃ ) 1.09 (s, 3H, CH—CH═C (C H ₃ ) ₂ ), 1.08 (s, 3H, CH—CH═C (C H ₃ ) ₂ ).

Polymerization Example: 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 12.5 ° C. with a DCPD: Ru ratio of (about 30,000: 1) (IMesH ₂ ) (C ₅ H Polymerization was carried out using ₅ N) ₂ (Cl) ₂ Ru═CH—CH═C (CH ₃ ) ₂ = 0.0123 grams. Result: Time to reach maximum temperature (T _max ) = 129 seconds. T _max = 197.1 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 157 ° C. Residual monomer ratio (toluene extraction at room temperature) = 2.13%.

(IMesH ₂ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru = CHPh (31) Synthesis Complex 1 (4.0 g, 4.7 mmol) was dissolved in toluene (10 mL) and pyridine (30 mL, 0.37 mol ) Was added. The reaction was stirred for about 10 minutes, during which time a color change from red to light green was observed. The reaction mixture was cannulated into 100 mL cold (−10 ° C.) pentane and a green solid precipitated. The precipitate was filtered, washed with 4 x 50 mL pentane and dried under reduced pressure to give 31 as a green powder (2.9 grams, 85% yield). Samples for elemental analysis were prepared by recrystallization from C ₆ H ₆ / pentane and then drying under reduced pressure. These samples are analyzed as monopyridine adduct (IMesH ₂ ) (C ₅ H ₅ N) (Cl) ₂ Ru═CHPh, possibly due to loss of pyridine under reduced pressure. ¹ H NMR (C ₆ D ₆ ): δ19.67 (s, 1H, CHPh), 8.84 (br.s, 2H, pyridine), 8.39 (br.s, 2H, pyridine), 8.07 (d, 2H, ortho CH, J _HH = 8 Hz), 7.15 (t, 1H, para CH, J _HH = 7 Hz), 6.83-6.04 (br.multipeak, 9H, pyridine, Mes CH), 3.37 (br.d, 4H, C H ₂ C H ₂ ), 2.79 (br. S, 6H, Mes CH ₃ ), 2.45 (br. S, 6H, Mes CH ₃ ), 2.04 (br. S, 6H, Mes CH ₃ ). C { ¹ H} NMR (C ₆ D ₆ ): δ314.90 (m, Ru = C HPh), 219.10 (s, Ru- C (N) ₂ ), 152.94, 150.84, 139.92, 138.38, 136.87, 135.99, 134.97, 131.10, 130.11, 129.88, 128.69, 123.38, 51.98, 51.37, 21.39, 20.96, 19.32. Analytical value for C ₃₃ H ₃₇ N ₃ C1 ₂ Ru: C, 61.20; H, 5.76; N, 6.49. Found: C, 61.25; H, 5.76; N, 6.58.

Typical synthesis of phosphine complexes:
IMesH ₂ ) (PPh ₃ ) (Cl) ₂ Ru = CHPh (41)
Complex 31 (150 mg, 0.21 mmol) and PPh ₃ (76 mg, 0.28 mmol) were combined in benzene (10 mL) and stirred for 10 minutes. The solvent was removed under reduced pressure and the resulting brown residue was washed with 4 × 20 mL pentane and dried under reduced pressure. Complex 41 was obtained as a brownish powder (125 mg, 73% yield). ³¹ P { ¹ H} NMR (C ₆ D ₆ ): δ 37.7 (s). ¹ H NMR (C ₇ D ₈ ): δ19.60 (s, ¹ H, Ru = C H Ph), 7.70 (d, 2H, ortho CH, J _HH = 8 Hz), 7.29-6.71 (multiple peaks, 20H, P Ph ₃ , Para C H , Meta C H , and Mes C H ), 6.27 (s, 2H, Mes CH), 3.39 (m, 4H, C H ₂ C H ₂ ), 2.74 (s, 6H, Ortho CH ₃ ), 2.34 (s, 6H, ortho CH ₃ ), 2.23 (s, 3H, para CH ₃ ), 1.91 (s, 3H, para CH ₃ ). ¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ305.34 (m, Ru- C HPh), 219.57 (d, Ru- C (N) ₂ , J _CP = 92 Hz), 151.69 (d, J _(CP = 4 Hz), 139.68, 138.35, 138.10, 138.97, 137.78, 135.89 135.21, 135.13, 131.96, 131.65, 131.36, 130.47, 129.83, 129.59 (d, J _CP = 2 Hz), 129.15, 128.92, 128.68, 128.00, 52.11 (d, J _CP = 4 Hz), 51.44 (d, J _CP = 2 Hz), 21.67, 21.35, 21.04, 19.21. _{C 46 H 47 N 2 C1 2} PRu analysis for: C, 66.50; H, 5.70 ; N, 3.37. Found: C, 66.82; H, 5.76; N, 3.29.

(IMesH ₂ ) (O ^t Bu) ₂ Ru = CHPh (42) Synthesis Complex 31 (7.5 mg, 0.010 mmol) and KOtBu (3 mg, 0.027 mmol) in C ₆ D ₆ (0.6 mL) under nitrogen Combined in NMR tube. The reaction mixture was allowed to stand for 15-20 minutes, during which time a color change from green to dark red was observed and an NMR spectrum was recorded after 30 minutes. ¹ H NMR (C ₆ D ₆ ): δ 16.56 (s, 1H, Ru = C H Ph), 7.63 (d, 2H, ortho CH, J _HH = 7 Hz), 7.2-7.1 (multiple peak, 3H, Meta C H and ortho C H ), 6.97 (s, 4H, Mes CH), 3.43 (s, 4H C H ₂ C H ₂ ), 2.59 (s, 12H, ortho CH ₃ ), 2.29 (s, 6H, para CH ₃ ), 1.18 (s, 18H, ^t Bu).

Synthesis of Tp (IMesH ₂ ) (Cl) Ru = CHPh (43)
KTp (87 mg, 0.34 mmol) and complex 31 (125 mg, 0.17 mmol) were combined in CH ₂ Cl ₂ (10 mL) and stirred for 1 hour. Pentane (20 mL) was added to precipitate the salt and the reaction was stirred for an additional 30 minutes before cannula filtration. The resulting light green solution was concentrated and the solid residue was washed with pentane (2 x 10 mL) and methanol (2 x 10 mL) and dried under reduced pressure to yield an analytically pure green powder. 43 (84 mg, 66% yield) was obtained. ¹ H NMR (CD ₂ C1 ₂ ): δ18.73 (s, 1H, Ru = C H Ph), 7.87 (d, 1H, Tp, J _HH = 2.4 Hz), 7.41 (d, 1H, Tp, J _HH = 2.1 Hz), 7.35-7.30 (multiple peaks, 3H, Tp and para CH), 7.08 (d, 1h, Tp, J _HH = 1.5 Hz), 6.82 (br.s, 5H, Mes C H , ortho C H And meta C H ), 6.24 (br.s, 3H, Mes CH), 6.16 (t, 1H, Tp, J _HH = 1.8 Hz) 5.95 (d, 1H, Tp, J _HH = 1.5 Hz), 5.69 (t , 1H, Tp, J _HH = 2.4 Hz), 5.50 (t, 1H, Tp, J _HH = 1.8 Hz), 3.77 (br.d, 4H, C H ₂ C H ₂ ), 2.91-0.893 (br. Peak, 18H, ortho C H ₃ , para C H ₃ ). ¹³ C { ¹ H} (CD ₂ C1 ₂ ): δ324.29 (m, Ru = C HPh), 220.57 (s, Ru- C (N) ₂ ), 151.50, 146.08, 145.39, 142.07, 137.94, 136.57, 134.41, 133.18, 130.60 (br), 129.55, 127.98, 106.41, 105.19, 104.51, 53.77 (br), 21.26, 20.32 (br). Analytical value for C ₃₇ H ₄₂ N ₈ C1BRu: C, 59.56; H, 5.67; N, 15.02. Found: C, 59.20; H, 5.67; N, 14.72.

Kinetics of the reaction of 1 with C ₅ D ₅ N A solution of 1 (0.88 mM) in toluene (1.6 mL) was prepared in a cuvette equipped with a rubber septum. This solution was temperature equilibrated at 20 ° C. in a UV-vis spectrometer. Pure pyridine-d ₅ (25-100 μL) was added via a microsyringe and the reaction rate was followed by monitoring the disappearance of the starting material (502 nm). For each scan, data was collected over 5 half-lives and fitted to a first order exponential function. Typical R ² values for exponential curve fitting were greater than 0.999.

The details of 31 X-ray crystal structures , intensity collection, and refinement are summarized in Table 1. Selected crystals were mounted on glass fibers using Palaton-N oil and transferred to a Bruker SMART 1000 CCD area detector equipped with a Crystal Logic CL24 low temperature device. Data were collected by ω scan at 7 φ values and subsequently processed with SAINT. Absorption correction or attenuation correction was not performed. Solve the structure using SHELXTL (by direct methods and difference Fourier maps subsequent), refinement was (least square method full matrix against F ^2). There were two molecules in the asymmetric unit. All non-hydrogen atoms were refined anisotropically and placed in calculated positions with U _iso values based on the U _eq of the atom to which the hydrogen atom was attached. Appropriate bond lengths and bond angles for certain molecules are presented in Table 2.

Synthesis of (IMes) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru = CHPh In a glove box filled with nitrogen, 0.120 g (0.142 mmol) of (IMes) (PCy ₃ ) Cl ₂ Ru = CHPh 1 Dissolved in mL of pyridine (large excess). The solution immediately turned green and was stirred at room temperature for 30 minutes. 20 mL of hexane was then added and the flask was stored at −10 ° C. overnight. The supernatant was removed from the green precipitate by decantation. The precipitate was washed twice with 20 mL hexane and dried under reduced pressure to give 0.080 g (78% yield) of light green product (IMes) (py) ₂ Cl ₂ Ru = CHPh .

¹ H NMR (499.852 MHz, CD ₂ Cl ₂ ): δ19.41 (s, 1H, CHPh), 8.74 (d, 2H, J = 7.5 Hz), 7.96 (d, 2H, J = 8.5 Hz), 7.70 ( d, 2H, J = 12.5 Hz), 7.55 (t, 1H, J = 12.5 Hz), 7.44 (t, 1H, J = 12 Hz), 7.33 (t, 1H, J = 12 Hz), 7.06 (m, 3H), 7.05 (s, 2H), 6.83 (m, 1H), 6.79 (s, 6H), 2.28 (s, 6H, para CH ₃ on Mes), 2.22 (br s, 12H, ortho CH on Mes ₃ ).

Characterization of (PCy ₃ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂
¹ H NMR (499.852 MHz, C ₆ D ₆ ): δ20.18 (overlapping dd, 1H, J = 10.3 Hz, Ru = CH), 9.14 (br s, 4H, pyridine), 8.07 (d, 1H , J = 11.5 Hz, -CH =), 6.68 (br s, 3H, pyridine), 6.43 (br m, 3H, pyridine), 2.54 (qt, 3H, J = 11.5 Hz, PCy ₃ ), 2.27 (d, 6H, J = 11.5 Hz, PCy3), 1.91 (qt, 6H, J = 12 Hz, PCy ₃ ), 1.78 (d, 6H, J = 10.5 Hz, PCy ₃ ), 1.62 (m, 4H, PCy ₃ ), 1.26 (s, 3H, CH ₃ ), 1.23 (m, 8H, PCy ₃ ), 0.75 (s, 3H, CH ₃ ). ³¹ P { ¹ H} NMR (121.392 MHz, C ₆ D ₆ ): δ 37.17 (s).

Observation of (Ph ₃ Tri) (C ₇ H ₁₀ N ₂ ) ₂ (Cl) ₂ Ru = CH-CH = C (CH ₃ ) ₂
0.020 g of (Ph ₃ Tri) (PCy ₃ ) (Cl) ₂ Ru = CH—CH═C (CH ₃ ) ₂ , 0.002 g of 4-dimethylaminopyridine (excess), and 0.060 mL of CD ₂ Cl ₂ Add to screw cap NMR tube. ¹ H NMR spectrum after 2 h at room temperature is a complete conversion to the desired product (Ph ₃ Tri) (C ₇ H ₁₀ N ₂ ) ₂ (Cl) ₂ Ru = CH—CH═C (CH ₃ ) ₂ Was showing.

¹ H NMR (499.852 MHz, C ₆ D ₆ ): δ 18.57 (d, 1H, J = 13 Hz, Ru = CH), 8.53 (d, J = 8 Hz), 7.84 (d, J = 6.5 Hz), 7.73-6.84 (multiple lines), 6.26 (d, J = 7 Hz), 6.09 (m), 6.04 (d, J = 10.5 Hz), 6.01 (d, J = 10.5 Hz), 5.42 (d, J = 10.5 Hz), 5.38 (d, J = 17.5 Hz), 3.22 (s), 3.01 (s), 2.99 (s), 1.73 (s), 1.23 (s).

(PCy ₃ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru═C═CHPh synthetic complex 44 (2.0 grams) was dissolved in toluene (10 mL), and pyridine (0.9 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₅ H ₅ N) ₂ ( Cl) ₂ Ru = C = CHPh (49) was obtained.

Example (1): 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 81.3 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (PCy ₃ ) (C Polymerization was carried out using ₅ H ₅ N) ₂ (Cl) ₂ Ru = C = CHPh = 0.0379 grams. Result: Time to reach maximum temperature (T _max ) = 97 seconds. T _max = 169.1 ° C.

Example (2): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0450 grams at a starting temperature of about 88.2 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru═C═CHPh = 0.0377 grams at a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 205 seconds. T _max = 249.7 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 164.77 ° C.

(PCy ₃ ) (C ₉ H ₁₂ N ₂ ) ₂ (Cl) ₂ Ru = C = CHPh Synthesis Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and 4-pyrrolidinopyridine (1.5 grams) was dissolved. Added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₉ H ₁₂ N ₂ ) as a light brown powder (1.9 grams, 95% yield) ₂ (Cl) ₂ Ru = C = CHPh (50) was obtained.

(PCy ₃ ) (C ₇ H ₁₀ N ₂ ) ₂ (Cl) ₂ Ru = C = CHPh Synthesis Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and 4-dimethylaminopyridine (1.3 grams) was dissolved. Added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₇ H ₁₀ N ₂ ) as a light brown powder (1.8 grams, 95% yield) ₂ (Cl) ₂ Ru = C = CHPh (51) was obtained.

(PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C = CHPh Synthetic Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and 4-phenylpyridine (1.2 grams) was added. . The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₁ H ₉ N) ₂ as a light brown powder (0.9 grams, 43% yield). (Cl) ₂ Ru = C = CHPh (52) was obtained.

Example (1): 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 79.4 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C = CHPh = 0.0455 grams was used for polymerization. Result: Time to reach maximum temperature (T _max ) = 90 seconds. T _max = 170.2 ° C.

Example (2): 75 gram mass of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0450 gram at a starting temperature of about 82.9 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru═C═CHPh = 0.0451 grams with a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 148 seconds. T _max = 242.1 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 158.28 ° C.

Example (3): a 75 g mass of hexyl norbornene, at a starting temperature of about 80.1 ° C., (about 15,000: 1) H _x N: In Ru ratio _{(PCy 3) (C 11 H} 9 N) 2 (Cl ) Polymerized using ₂ Ru = C = CHPh = 0.244 grams. Result: Time to reach maximum temperature (T _max ) = 391 seconds. T _max = 155.4 ° C.

Example (4): 75 grams of hexyl norbornene, (15,000: 1: 2) H _x N: Ru: s-ImesHCCl in the presence of s-ImesHCCl3 = 0.0240 g at a starting temperature of about 81.7 ° C Polymerization was performed using (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C = CHPh = 0.246 gram in ₃ ratios. Result: Time to reach maximum temperature (T _max ) = 224 seconds. T _max = 193.9 ° C.

Example (5): A 75 g mass monomer mixture prepared by mixing 37.5 g DCPD (with 24 wt% trimerized DCPD) and 37.5 g hexylnorbornene together, by heating to a starting temperature, (15,000: 1) DCPD of: Ru reactant ratio and (15,000: 1) H _x N: in Ru reactant ratio _{(PCy 3) (C 11 H} 9 N) 2 (Cl ) Polymerization was carried out using ₂ Ru = C = CHPh = 0.0276 g. Result: Time to reach maximum temperature (T _max ) = 195 seconds. T _max = 148.8 ° C.

Example (6): A 75 g mass monomer mixture prepared by mixing 37.5 g DCPD (with 24 wt% trimerized DCPD) and 37.5 g hexylnorbornene together, By heating to the starting temperature, in the presence of s-ImesHCCl ₃ = 0.0269 g, (15,000: 1: 2) DCPD: Ru: s-ImesHCCl ₃ reactant ratio and (15,000: 1: 2) H _x Polymerization was performed using (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru═C═CHPh = 0.0275 g with N: Ru: s-ImesHCCl ₃ reactant ratio. Result: Time to reach maximum temperature (T _max ) = 180 seconds. T _max = 217.3 ° C.

_{(PCy 3) (C 5 H} 5 N) 2 a _{(Cl) 2 Ru = C =} CH-C (CH 3) 3 Synthesis Complex 44 (2.0 grams) was dissolved in toluene (10 mL), pyridine (0.9 g ) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₅ H ₅ N) ₂ ( Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ (53) was obtained.

Example (1): A 75 gram mass of DCPD (containing about 24% trimerized DCPD) at a starting temperature of about 79.5 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (PCy ₃ ) (C Polymerization was carried out using ₅ H ₅ N) ₂ (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ = 0.0370 grams. Result: Time to reach maximum temperature (T _max ) = 155 seconds. T _max = 207.4 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 70.73 ° C.

Example (2): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0446 grams at a starting temperature of about 82.2 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ = 0.0368 grams at a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 76 seconds. T _max = 239.7 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 178.83 ° C.

Example (3): 75 grams of hexylnorbornene at a starting temperature of about 82.4 ° C. with a H _x N: Ru ratio of (20,000: 1) (PCy ₃ ) (C ₅ H ₅ N) ₂ (Cl) Polymerization was carried out using ₂ Ru = C = CH-C (CH ₃ ) ₃ = 0.0148 grams. Result: Time to reach maximum temperature (T _max ) = 212 seconds. T _max = 189.4 ° C.

Example (4): 75 grams of hexylnorbornene at a starting temperature of about 80.9 ° C. in the presence of s-ImesHCCl3 = 0.0092 g of (20,000: 1: 1) H _x N: Ru: s-ImesHCCl (PCy ₃₎ were _{(C 5 H 5 N) 2} (Cl) 2 Ru = C = CH-C (CH 3) polymerization using a ₃ = 0.0149 g at ₃ ratio. Result: Time to reach maximum temperature (T _max ) = 154 seconds. T _max = 194.5 ° C.

Example (5): A 75 g mass monomer mixture prepared by mixing 37.5 g DCPD (with 24 wt% trimerized DCPD) and 37.5 g hexylnorbornene together, by heating to a starting temperature, (20,000: 1) DCPD of: Ru reactant ratio and (20,000: 1) H _x N: in Ru reactant ratio _{(PCy 3) (C 5 H} 5 N) 2 (Cl ) ₂ Ru = C = CH—C (CH ₃ ) ₃ = 0.0163 g was used for polymerization. Result: Time to reach maximum temperature (T _max ) = 149 seconds. T _max = 191.5 ° C.

Example (6): A 75 g mass monomer mixture prepared by mixing 37.5 g DCPD (with 24 wt% trimerized DCPD) and 37.5 g hexylnorbornene together, By heating to the starting temperature, in the presence of s-ImesHCCl ₃ = 0.0100 g, (20,000: 1: 2) DCPD: Ru: s-ImesHCCl ₃ reactant ratio and (20,000: 1: 2) H _x Polymerization was performed using (PCy ₃ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ = 0.0163 g at a N: Ru: s-ImesHCCl ₃ reactant ratio. Result: Time to reach maximum temperature (T _max ) = 169 seconds. T _max = 221.3 ° C.

(PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru = C = CHPh Synthetic Complex 44 (2.0 grams) dissolved in toluene (10 mL) and 4,4′-bipyridine (1.5 grams) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ as an orange powder (1.9 grams, 90% yield). (Cl) ₂ Ru = C = CHPh (54) was obtained.

Example (1): A 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 82.7 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (PCy ₃ ) (C Polymerization was performed using ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru = C = CHPh = 0.0457 grams. Result: Time to reach maximum temperature (T _max ) = 246 seconds. T _max = 159.9 ° C.

Example (2): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0448 grams at a starting temperature of about 82.3 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru = C = CHPh = 0.0462 grams with a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 244 seconds. T _max = 230.0 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 126.38 ° C.

(PCy ₃ ) (C ₁₂ H ₈ N ₂ ) (Cl) ₂ Ru = C = CHPh Complex Complex 44 (2.0 grams) is dissolved in toluene (10 mL) and 1,10-phenanthroline (0.9 grams) is added. did. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₂ H ₈ N ₂ ) as an orange powder (1.9 grams, 90% yield). Cl) ₂ Ru = C = CHPh (55) was obtained.

¹ H NMR (500 MHz, CD ₂ Cl ₂ ): δ = 6.98-10.18 (multiple peak, 13H), 5.03 (d, 1H, J = 4 Hz, vinylidene peak), 0.95-2.70 (multiple peak, 33H) ppm.

(PCy ₃ ) (C ₁₀ H ₈ N ₂ ) (Cl) ₂ Ru = C = CHPh Synthesis Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and 2,2'-bipyridine (0.8 grams) was dissolved. Added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) as a green powder (1.6 grams, 94% yield) ( Cl) ₂ Ru = C = CHPh (56) was obtained.

(PCy ₃ ) (C ₁₈ H ₁₂ N ₂ ) ₂ (Cl) ₂ Ru = C = CHPh Complex Complex 44 (2.0 grams) was dissolved in toluene (10 mL) and 2,2'-biquinoline (1.2 grams) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₈ H ₁₂ N ₂ ) ₂ as a purple powder (1.7 grams, 89% yield). (Cl) ₂ Ru = C = CHPh (57) was obtained.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ = 6.88-9.15 (multiple peak, 17H), 4.79 (d, 1H, J = 3 Hz, vinylidene), 1.21-2.86 (multiple peak, 33H) ppm.

_{(PCy 3) (C 9 H} 12 N 2) 2 (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 45 (2.0 grams) was dissolved in toluene (10 mL), 4-pylori Dinopyridine (1.5 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₉ H ₁₂ N ₂ ) as a dark green powder (1.8 grams, 90% yield) ₂ (Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ (58) was obtained.

(PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru = C = CH-C (CH ₃ ) ₃ synthesis complex 45 (2.0 g) was dissolved in toluene (10 mL), and 4,4 '-Bipyridine (1.5 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ as a brown powder (1.7 grams, 81% yield). (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (59) was obtained.

Example (1): 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 81.2 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (PCy ₃ ) (C Polymerization was performed using ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ = 0.0451 grams. Result: Time to reach maximum temperature (T _max ) = 349 seconds. T _max = 157.7 ° C.

Example (2): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0445 grams at a starting temperature of about 80.8 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ = 0.0447 grams with a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 189 seconds. T _max = 208.4 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 95.70 ° C.

_{(PCy 3) (C 11 H} 9 N) 2 (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 45 (2.0 grams) was dissolved in toluene (10 mL), 4-phenylpyridine (1.6 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₁ H ₉ N) ₂ ( Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (60) was obtained.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ = 6.89-10.08 (multipeak, 18H), 4.17 (d, 1H, J = 4 Hz, vinylidene), 1.25-2.74 (multipeak, 33H), 1.31 (s, 9H) ppm.

Example (1): 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 82.0 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ = 0.0443 grams were used for polymerization. Result: Time to reach maximum temperature (T _max ) = 208 seconds. T _max = 205.1 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 54.42 ° C.

Example (2): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0449 grams at a starting temperature of about 81.1 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ = 0.0445 grams at a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 126 seconds. T _max = 246.2 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 175.35 ° C.

_{(PCy 3) (C 12 H} 8 N 2) (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 45 (2.0 grams) was dissolved in toluene (10 mL), 1,10- Phenanthroline (0.9 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₂ H ₈ N ₂ ) as an orange powder (1.5 grams, 83% yield) ( Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ (61) was obtained.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ = 6.90-10.73 (multipeak, 8H), 4.02 (d, 1H, J = 3 Hz, vinylidene), 1.46-3.06 (multipeak, 33H), 1.62 (s, 9H) ppm.

_{(PCy 3) (C 10 H} 8 N 2) (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 45 (2.0 grams) was dissolved in toluene (10 mL), 2, 2 ' -Bipyridine (0.8 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) as an orange powder (1.3 grams, 76% yield). Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ (62) was obtained.

(PCy ₃₎ a _{(C 18 H 12 N 2)} 2 (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 45 (2.0 grams) was dissolved in toluene (10 mL), 2, 2 '-Biquinoline (1.3 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₈ H ₁₂ N ₂ ) ₂ as a gray powder (1.1 grams, 58% yield). (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (63) was obtained.

(IMesH ₂ ) (C ₉ H ₁₂ N ₂ ) ₂ (Cl) ₂ Ru = C = CH-C (CH ₃ ) ₃ Synthesis Complex 46 (2.0 g) was dissolved in toluene (10 mL) Dinopyridine (1.4 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₉ H ₁₂ N ₂ ) ₂ as a gray powder (0.7 grams, 35% yield). (Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ (64) was obtained.

Example (1): A 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 80.7 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (IMesH ₂ ) (C ₉ H ₁₂ N ₂ ) ₂ (Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ = 0.0456 grams were used for polymerization. Result: Time to reach maximum temperature (T _max ) = 143 seconds. T _max = 170.5 ° C.

(IMesH ₂₎ the _{(C 10 H 8 N 2)} 2 (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 46 (2.0 grams) was dissolved in toluene (10 mL), 4, 4 '-Bipyridine (1.5 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ as a dark purple powder (2.0 grams, 95% yield). (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (65) was obtained.

Example (1): 75 grams of hexyl norbornene (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ (at a starting temperature of about 80.6 ° C. with an H _x N: Ru ratio of (about 7,500: 1) Polymerization was performed using Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ = 0.0488 grams. Result: Time to reach maximum temperature (T _max ) = 183 seconds. T _max = 191.7 ° C.

Example (2): A 75 g mass monomer mixture prepared by mixing 37.5 g DCPD (with 24 wt% trimerized DCPD) and 37.5 g hexylnorbornene together, By heating to the starting temperature, (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ ((7,500: 1) DCPD: Ru reactant ratio and (7,500: 1) H _x N: Ru reactant ratio) Polymerization was carried out using Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ = 0.0549 g. Result: Time to reach maximum temperature (T _max ) = 183 seconds. T _max = 181.9 ° C.

(IMesH ₂ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C = CH-C (CH ₃ ) ₃ Synthesis Complex 46 (2.0 g) was dissolved in toluene (10 mL) and 4-phenylpyridine was dissolved. (1.5 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₁ H ₉ N) ₂ as a light brown powder (0.6 grams, 29% yield). (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (66) was obtained.

(IMesH ₂ ) (C ₅ H ₅ N) ₂ (Cl) ₂ Ru = C = CH-C (CH ₃ ) ₃ Synthetic complex 46 (2.0 g) was dissolved in toluene (10 mL) and pyridine (0.8 g ) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₅ H ₅ N) ₂ ( Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (67) was obtained.

_{(IMesH 2) (C 10 H} 8 N 2) (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 46 (2.0 grams) was dissolved in toluene (10 mL), 2, 2 ' -Bipyridine (0.8 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) as a brown powder (0.9 grams, 53% yield). Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ (68) was obtained.

_{(PCy 3) (C 5 H} 5 N) 2 (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 47 (2.0 grams) was dissolved in toluene (10 mL), pyridine (0.4 grams) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₅ H ₅ N) ₂ (PCy ₃ ) as a brown powder (0.7 grams, 41% yield). Cl) ₂ Ru = C = C = C (Ph) ₂ (69) was obtained.

(PCy ₃₎ a _{(C 7 H 10 N 2)} 2 (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 45 (2.0 grams) was dissolved in toluene (10 mL), 4-dimethyl Aminopyridine (1.2 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₇ H ₁₀ N ₂ ) ₂ as a pink powder (1.6 grams, 84% yield). (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (70) was obtained.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ = 5.89-9.66 (multipeak, 8H), 4.14 (d, J = 4 Hz, vinylidene), 1.31-2.78 (multipeak, 45H), 1.40 (s , 9H) ppm.

Example (1): 75 grams of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 81.2 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (PCy ₃ ) (C ₇ H ₁₀ N ₂ ) ₂ (Cl) ₂ Ru = C═CH—C (CH ₃ ) ₃ = 0.0410 grams was used for polymerization. Result: Time to reach maximum temperature (T _max ) = 306 seconds. T _max = 189.6 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 35.88 ° C.

Example (2): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0450 grams at a starting temperature of about 81.9 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₇ H ₁₀ N ₂ ) ₂ (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ = 0.0411 grams at a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 161 seconds. T _max = 246.5 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 169.56 ° C.

(IMesH ₂₎ a _{(C 7 H 10 N 2)} 2 (Cl) 2 Ru = C = CH-C (CH 3) 3 Synthesis Complex 46 (2.0 grams) was dissolved in toluene (10 mL), 4-dimethyl Aminopyridine (1.2 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₇ H ₁₀ N ₂ ) ₂ as a gray powder (0.9 grams, 47% yield). (Cl) ₂ Ru═C═CH—C (CH ₃ ) ₃ (71) was obtained.

(PCy ₃₎ a _{(C 7 H 10 N 2)} 2 (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 47 (2.0 grams) was dissolved in toluene (10 mL), 4-dimethylamino Pyridine (1.1 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₇ H ₁₀ N ₂ ) ₂ as a brown powder (1.3 grams, 68% yield). (Cl) ₂ Ru = C = C = C (Ph) ₂ (72) was obtained.

(PCy ₃₎ a _{(C 12 H 8 N 2)} (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 47 (2.0 grams) was dissolved in toluene (10 mL), 1,10-phenanthroline (0.8 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₂ H ₈ N ₂ ) as a reddish brown powder (1.2 grams, 67% yield). Cl) ₂ Ru = C = C = C (Ph) ₂ (73) was obtained.

(PCy ₃₎ a _{(C 11 H 9 N) 2} (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 47 (2.0 grams) was dissolved in toluene (10 mL), 4-phenylpyridine ( 1.4 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (PCy ₃ ) as a dark purple powder (1.5 grams, 71% yield). Cl) ₂ Ru = C = C = C (Ph) ₂ (74) was obtained.

Example (1): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0447 grams at a starting temperature of about 83.8 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru═C═C═C (Ph) ₂ = 0.0499 grams with a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 288 seconds. T _max = 238.7 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 124.72 ° C.

Example (2): 75 gram mass of hexyl norbornene at a starting temperature of about 80.3 ° C. with (7,500: 1: 2) H _x N: Ru: s-IMesHCCl ₃ ratio (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C = C = C (Ph) ₂ = 0.0536 grams was used for polymerization. Result: Time to reach maximum temperature (T _max ) = 230 seconds. T _max = 195.6 ° C.

Example (3): A 75 g mass monomer mixture prepared by mixing 37.5 g DCPD (with 24 wt% trimerized DCPD) and 37.5 g hexyl norbornene together, By heating to the starting temperature, (7,500: 1: 2) DCPD: Ru: s-IMesHCCl ₃ reactant ratio and (7,500: 1: 2) H _x N: Ru: s-IMesHCCl ₃ reactant ratio. Polymerization was carried out using (PCy ₃ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru═C═C═C (Ph) ₂ = 0.0599 g. Result: Time to reach maximum temperature (T _max ) = 178 seconds. T _max = 220.8 ° C.

_{(PCy 3) (C 10 H} 8 N 2) 2 (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 47 (2.0 grams) was dissolved in toluene (10 mL), 4, 4 ' -Bipyridine (1.4 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ as a reddish brown powder (2.0 grams, 95% yield). (Cl) ₂ Ru = C = C = C (Ph) ₂ (75) was obtained.

Example (1): 75 grams of DCPD (including about 24% trimerized DCPD) in the presence of sIMesHCCl ₃ = 0.0448 grams at a starting temperature of about 84.6 ° C. (about 10,000: 1: 2) Polymerization was performed using (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru═C═C═C (Ph) ₂ = 0.0500 grams with a DCPD: Ru: sIMesHCCl ₃ ratio of Result: Time to reach maximum temperature (T _max ) = 190 seconds. T _max = 224.7 ° C. Glass transition temperature measured by thermomechanical analysis (TMA) = 105.52 ° C.

_{(PCy 3) (C 9 H} 12 N 2) 2 (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 47 (2.0 grams) was dissolved in toluene (10 mL), 4-pyrrolidino Pyridine (1.3 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₉ H ₁₂ N ₂ ) ₂ as a dark purple powder (1.4 grams, 70% yield). (Cl) ₂ Ru = C = C = C (Ph) ₂ (76) was obtained.

The _{(PCy 3) (C 10 H} 8 N 2) (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 47 (2.0 grams) was dissolved in toluene (10 mL), 2,2' Bipyridine (0.7 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL of cold pentane and dried under reduced pressure to give (PCy ₃ ) (C ₁₀ H ₈ N ₂ ) as a dark purple powder (1.1 grams, 65% yield) ( Cl) ₂ Ru = C = C = C (Ph) ₂ (77) was obtained.

_{(IMesH 2) (C 5 H} 5 N) 2 (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 48 (2.0 grams) was dissolved in toluene (10 mL), pyridine (0.4 grams) Was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₅ H ₅ N) ₂ ( Cl) ₂ Ru = C = C = C (Ph) ₂ (78) was obtained.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ = 6.52-8.09 (multiple peaks, 20H), 4.00 (s, 4H, sIMes) 1.00-2.28 (multiple peaks 18H) ppm.

(IMesH ₂₎ a _{(C 7 H 10 N 2)} 2 (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 48 (2.0 grams) was dissolved in toluene (10 mL), 4-dimethylamino Pyridine (1.0 gram) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 x 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₇ H ₁₀ N ₂ ) ₂ as a reddish brown powder (1.0 gram, 53% yield). (Cl) ₂ Ru = C = C = C (Ph) ₂ (79) was obtained.

(IMesH ₂₎ the _{(C 12 H 8 N 2)} (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 48 (2.0 grams) was dissolved in toluene (10 mL), 1,10-phenanthroline (0.8 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₂ H ₈ N ₂ ) as a red powder (0.6 grams, 33% yield). Cl) ₂ Ru = C = C = C (Ph) ₂ (80) was obtained.

(IMesH ₂ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C = C = C (Ph) ₂ Synthesis Complex 48 (2.0 grams) was dissolved in toluene (10 mL) and 4-phenylpyridine ( 1.3 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₁ H ₉ N) ₂ ( Cl) ₂ Ru = C = C = C (Ph) ₂ (81) was obtained.

Example (1): A 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 80.9 ° C. (IMesH ₂ ) (C ₁₁ H ₉ N) ₂ (Cl) ₂ Ru = C = C = C (Ph) ₂ = 0.0515 grams was used for polymerization. Result: Time to reach maximum temperature (T _max ) = 275 seconds. T _max = 118.2 ° C.

_{(IMesH 2) (C 10 H} 8 N 2) 2 (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 48 (2.0 grams) was dissolved in toluene (10 mL), 4, 4 ' -Bipyridine (1.3 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ as a brown powder (1.9 grams, 90% yield). (Cl) ₂ Ru = C = C = C (Ph) ₂ (82) was obtained.

Example (1): A 75 gram mass of DCPD (including about 24% trimerized DCPD) at a starting temperature of about 80.1 ° C. with a DCPD: Ru ratio of (about 10,000: 1) (IMesH ₂ ) (C Polymerization was performed using ₁₀ H ₈ N ₂ ) ₂ (Cl) ₂ Ru = C = C = C (Ph) ₂ = 0.0512 grams. Result: Time to reach maximum temperature (T _max ) = 144 seconds. T _max = 138.8 ° C.

Example (2): 75 grams of hexyl norbornene (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ at a starting temperature of about 80.3 ° C. with an H _x N: Ru reactant ratio of (7,500: 1) Polymerization was performed using (Cl) ₂ Ru = C = C = C (Ph) ₂ = 0.0552 grams. Result: Time to reach maximum temperature (T _max ) = 578 seconds. T _max = 138.5 ° C.

Example (3): A 75 g mass monomer mixture prepared by mixing together 37.5 g DCPD (with 24 wt% trimerized DCPD) and 37.5 g hexylnorbornene, the mixture is about 80.6 ° C. By heating to the starting temperature, (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) ₂ ((7,500: 1) DCPD: Ru reactant ratio and (7,500: 1) H _x N: Ru reactant ratio) Polymerization was carried out using Cl) ₂ Ru = C = C = C (Ph) ₂ = 0.0617 g. Result: Time to reach maximum temperature (T _max ) = 259 seconds. T _max = 135.7 ° C.

(IMesH ₂₎ the _{(C 10 H 8 N 2)} (Cl) 2 Ru = C = C = C (Ph) 2 Synthesis Complex 48 (2.0 grams) was dissolved in toluene (10 mL), 2,2' Bipyridine (0.7 grams) was added. The reaction flask was purged with argon and the reaction mixture was stirred at about 20 ° C. to about 25 ° C. for about 12 hours. After about 12 hours, the reaction mixture was transferred into 75 mL of cold (about 0 ° C.) pentane. The pentane mixture was filtered, washed with 4 × 20 mL of cold pentane and dried under reduced pressure to give (IMesH ₂ ) (C ₁₀ H ₈ N ₂ ) as a brown powder (1.3 grams, 76% yield). Cl) ₂ Ru = C = C = C (Ph) ₂ (83) was obtained.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ = 6.60-7.85 (multipeak, 18H), 4.00 (s, 4H, sIMes) 1.08-2.60 (multipeak, 18H) ppm.

Claims (30)

Cyclic or acyclic olefins and the formula:

(Where
M is a ruthenium-time;
X and X ¹ are each independently a halide, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ selected from the group consisting of CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate;
L is an N-heterocyclic carbene ligand or phosphine;
L ^{1 ′} and L ² may be the same or different and each is a substituted or unsubstituted heteroarene;
R is hydrogen and R ¹ is selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, and aryl )
A process for metathesis of cyclic or acyclic olefins, comprising contacting with a compound of: X and X ¹ are each Cl, L is (IMesH ₂ ) or phosphine, L ^{1 ′} and L ² are each independently pyridine or a pyridine derivative, R is hydrogen, and R ¹ is phenyl or vinyl. The method of claim 1 , wherein Cyclic olefins and the formula:

(Where
M is ruthenium or osmium;
X and X ¹ are each independently a halide, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ selected from the group consisting of CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate;
L is any neutral electron donor ligand;
L ^{1 ′} and L ² may be the same or different and each is a substituted or unsubstituted heteroarene;
R is hydrogen and R ¹ is selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, and aryl)
A method for ring-opening metathesis polymerization of cyclic olefins comprising contacting with a compound of: The method according to claim 3 , wherein the olefin is a substituted or unsubstituted norbornene or norbornene-type monomer or a derivative thereof. The method according to claim 4 , wherein the olefin is substituted or unsubstituted dicyclopentadiene. The method according to claim 4 , wherein the olefin is one or more kinds of substituted or unsubstituted norbornene or norbornene type monomers or a mixture of derivatives thereof. formula:

And a compound of the formula:

(here,
M is ruthenium or osmium;
X and X ¹ may be the same or different and are each independently any anionic ligand;
L, L ^{1 ′} and L ² may be the same or different and are each independently any neutral electron donor ligand;
R, R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and are each independently hydrogen or C ₁ -C ₂₀ alkyl, C _2- C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, aryl, C ₁ -C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C ₂₀ alkenyloxy, C ₂ -C ₂₀ alkynyloxy, aryloxy, C ₂ - C ₂₀ alkoxycarbonyl, it is a C ₁ -C ₂₀ alkylthio, C ₁ -C ₂₀ alkylsulfonyl and C ₁ -C ₂₀ alkylsulfinyl and substituted or unsubstituted substituents selected from the group consisting of silyl; and
A is hydrogen, Si, Sn, Li, Na, MgX ³ and acyl, where X ³ is any halogen, B is CCl ₃ ; CH ₂ SO ₂ Ph; C ₆ F ₅ ; OR ²¹ ; and N (R ²² ) (R ²³ ), wherein R ²¹ is Me, C ₂ H ₅ , iC ₃ H ₇ , CH ₂ CMe ₃ , CMe ₃ , C ₆ H ₁₁ (cyclohexyl), CH ₂ Ph, CH ₂ norbornyl, CH ₂ norbornenyl, C ₆ H ₅ , 2,4,6- (CH ₃ ) ₃ C ₆ H ₂ (mesityl), 2,6-i-Pr ₂ C ₆ H ₂ , 4- Selected from the group consisting of Me-C ₆ H ₄ (tolyl), 4-Cl—C ₆ H ₄ ; R ²² and R ²³ are each independently Me, C ₂ H ₅ , iC ₃ H ₇ , CH ₂ CMe ₃ , CMe ₃ , C ₆ H ₁₁ (cyclohexyl), CH ₂ Ph, CH ₂ norbornyl, CH ₂ norbornenyl, C ₆ H ₅ , 2,4,6- (CH ₃ ) ₃ C ₆ H ₂ (mesityl), 2, (Selected from the group consisting of 6-i-Pr ₂ C ₆ H ₂ , 4-Me-C ₆ H ₄ (tolyl), 4-Cl-C ₆ H ₄ )
A method for polymerizing an olefin, comprising contacting a compound of the above with a cyclic or acyclic olefin. M is ruthenium;
X and X ¹ are each independently a halide, CF ₃ CO ₂ , CH ₃ CO ₂ , CFH ₂ CO ₂ , (CH ₃ ) ₃ CO, (CF ₃ ) ₂ (CH ₃ ) CO, (CF ₃ ) (CH ₃ ) ₂ selected from the group consisting of CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate;
L is any neutral electron donor ligand;
L ^{1 ′} and L ² may be the same or different and each is a substituted or unsubstituted heteroarene;
R is hydrogen and R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, and aryl. Selected from the group;
A is hydrogen, B is CCl _3, The method of claim 7. The method according to claim 7 , wherein the olefin is a substituted or unsubstituted norbornene or norbornene type monomer or a derivative thereof. The method according to claim 7 , wherein the olefin is substituted or unsubstituted dicyclopentadiene. The method according to claim 7 , wherein the olefin is one or more substituted or unsubstituted norbornene or norbornene type monomers or a mixture of derivatives thereof. formula:

(Where
M is ruthenium or osmium;
X and X ¹ Can be the same or different and are each independently any anionic ligand;
L is an N-heterocyclic carbene ligand or phosphine; ^{1 '} And L ² Each is a heterocyclic ligand;
R and R ¹ May be the same or different and each independently represents hydrogen or C ₁ -C ₂₀ Alkyl, C ₂ -C ₂₀ Alkenyl, C ₂ -C ₂₀ Alkynyl, aryl, C ₁ -C ₂₀ Carboxylate, C ₁ -C ₂₀ Alkoxy, C ₂ -C ₂₀ Alkenyloxy, C ₂ -C ₂₀ Alkynyloxy, aryloxy, C ₂ -C ₂₀ Alkoxycarbonyl, C ₁ -C ₂₀ Alkylthio, C ₁ -C ₂₀ Alkylsulfonyl, C ₁ -C ₂₀ A substituted or unsubstituted substituent selected from the group consisting of alkylsulfinyl and silyl)
Compound. R and R ¹ At least one of the substituents is C ₁ -C _Ten Alkyl, C ₁ -C _Ten The compound according to claim 12, which is substituted with one or more groups selected from the group consisting of alkoxy and aryl, and the groups are substituted or unsubstituted. The group is halogen, C ₁ -C _Five Alkyl, C ₁ -C _Five 14. A compound according to claim 13 substituted with one or more groups selected from the group consisting of alkoxy and phenyl. R is hydrogen and R ¹ Is C ₁ -C ₂₀ Alkyl, C ₂ -C ₂₀ 13. A compound according to claim 12, selected from the group consisting of alkenyl and aryl. R ¹ 16. A compound according to claim 15, wherein is phenyl or vinyl. X and X ¹ Are each independently hydrogen, halide, or C ₁ -C ₂₀ Alkyl, aryl, C ₁ -C ₂₀ Alkoxide, aryloxide, C _Three -C ₂₀ Alkyl diketonates, aryl diketonates, C ₁ -C ₂₀ Carboxylate, aryl sulfonate, C ₁ -C ₂₀ Alkyl sulfonate, C ₁ -C ₂₀ Alkylthio, C ₁ -C ₂₀ Alkylsulfonyl or C ₁ -C ₂₀ Selected from the group consisting of alkylsulfinyl and X and X ¹ 13. A compound according to claim 12, wherein each is independently substituted or unsubstituted. X and X ¹ At least one of C ₁ -C _Ten Alkyl, C ₁ -C _Ten 18. A compound according to claim 17, which is substituted with one or more groups selected from the group consisting of alkoxy and aryl, and the groups are substituted or unsubstituted. The group is halogen, C ₁ -C _Five Alkyl, C ₁ -C _Five 19. A compound according to claim 18 substituted with one or more groups selected from the group consisting of alkoxy and phenyl. X and X ¹ Are each independently halide, benzoate, C ₁ -C _Five Carboxylate, C ₁ -C _Five Alkyl, phenoxy, C ₁ -C _Five Alkoxy, C ₁ -C _Five Alkylthio, aryl, and C ₁ -C _Five 13. A compound according to claim 12, selected from the group consisting of alkyl sulfonates. X and X ¹ Are each independently halide, CF _Three CO ₂ , CH _Three CO ₂ , CFH ₂ CO ₂ , (CH _Three ) _Three CO, (CF _Three ) ₂ (CH _Three ) CO, (CF _Three ) (CH _Three ) ₂ 21. The compound of claim 20, selected from the group consisting of CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate. An N-heterocyclic carbene ligand has the formula:

(Where R, R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^Ten And R ¹¹ Are each independently hydrogen or C ₁ -C ₂₀ Alkyl, C ₂ -C ₂₀ Alkenyl, C ₂ -C ₂₀ Alkynyl, aryl, C ₁ -C ₂₀ Carboxylate, C ₁ -C ₂₀ Alkoxy, C ₂ -C ₂₀ Alkenyloxy, C ₂ -C ₂₀ Alkynyloxy, aryloxy, C ₁ -C ₂₀ Alkoxycarbonyl, C ₁ -C ₂₀ Alkylthio, C ₁ -C ₂₀ Alkylsulfonyl and C ₁ -C ₂₀ A substituted or unsubstituted substituent selected from the group consisting of alkylsulfinyl)
14. The compound of claim 13, selected from the group consisting of: L ^{1 '} And L ² 13. A compound according to claim 12, wherein at least one of is aromatic. L ^{1 '} And L ² 13. A compound according to claim 12, wherein together form a bidentate ligand. L ^{1 '} And L ² At least one of furan, thiophene, pyrrole, pyridine, bipyridine, picolilymine, γ-pyran, γ-thiopyran, phenanthroline, pyrimidine, bipyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benz Selected from the group consisting of imidazole, oxazole, thiazole, dithiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine, bisimidazole and bisoxazole. The compound according to claim 12, which is a substituted or unsubstituted heteroarene. L ^{1 '} And L ² 26. The compound of claim 25, wherein at least one of is a substituted or unsubstituted pyridine or a substituted or unsubstituted pyridine derivative. A substituted or unsubstituted heteroarene has the formula:

26. The compound of claim 25, selected from the group consisting of: L ^{1 '} And L ² At least one of the formulas:

(Where R is C ₁ -C ₂₀ (Selected from the group consisting of alkyl, aryl, ether, amide, halide, nitro, ester, pyridyl)
The compound according to claim 12, which is a substituted or unsubstituted heterocycle selected from the group consisting of: X and X ¹ Are each Cl and L is (IMesH ₂ ) And L ^{1 '} And L ² Are each independently pyridine or a pyridine derivative, R is hydrogen, R ¹ 13. A compound according to claim 12, wherein is phenyl or vinyl. formula:

(Where sIMES or IMesH ₂ Is

Is)
A compound selected from the group consisting of: