BR102013016146A2 - process for producing a silylated product by dehydrogenation, composition, compound and process for producing a crosslinked material - Google Patents

Abstract

"Process for Producing a Dehydrogenation Silylated Product, Composition, Compound, and Process for Producing a Crosslinked Material" Disclosed herein are cobalt complexes containing dented pyridine diimine binders and their use as efficient and selective dehydrogenation and crosslinked silylation catalysts.

Description

Field of the Invention In general, this invention relates to transition metal-containing compounds, more specifically to cobalt complexes containing diimine binders. "Process for Producing a Silylated Product by Dehydrogenation, Compounding, Compound, and Process for Producing a Crosslinked Material" pyridine and its use as efficient dehydrogenation crosslinking and silylation catalysts.

Background of the Invention Hydrosilylation chemistry, typically involving a reaction between a silyl hydride and an unsaturated organic group, is the basis for synthetic pathways to produce commercial silicone based products such as silicone surfactants, silicone fluids as well as many others. cured addition products such as sealants, adhesives, and silicone based coatings. See, for example, U.S. Patent Application Publication 2001 / 0009573A1 to Delis et al. Typical hydrosilylation reactions use precious metal catalysts to catalyze the addition of a silyl hydride (Si-H) to an unsaturated group, such as an olefin. In these reactions, the resulting product is a silyl substituted saturated compound. In most of these cases, the addition of the silyl group proceeds in an anti-Markovnikov manner, that is, at the less substituted carbon atom of the unsaturated group. Most precious metal catalysed hydrosilylations only work well with terminal unsaturated olefins, since internal unsaturation is generally unreactive or only very unreactive. Currently, there are only limited methods for general olefin hydrosilylation where after the addition of the Si-H group an unsaturation remains on the original substrate. This reaction called dehydrogenation silylation has potential uses in the synthesis of new silicone materials such as silanes, silicone fluids, cross-linked silicone elastomers, and cross-linked silicone or silylated polymers such as polyolefins, unsaturated polyesters and the like. Various precious metal complex catalysts are known in the art. For example, U.S. Patent No. 3,775,452 discloses a platinum complex containing unsaturated siloxanes as binders. This type of catalyst is known as Karstedt catalyst. Other exemplary platinum-based hydrosilylation catalysts that have been described in the literature include Ashby catalyst disclosed in US Patent No. 3,159,601, Lamoreaux catalyst disclosed in US Patent No. 3,220,972, and Speier catalyst disclosed in Speier JL, Webster JA and Barbes GH, J. Am. Chem. Soc. 79, 974 (1957). There are examples of the use of Fe (CO) 5 to promote dehydrogenation hydrosilylation and silylation. (See Nesmeyanov, AN; Freidlina, R. Kh.; Chukovskaya, EC; Petrova, RG; Belyavsky, AB Tetrahedron 1962, 17, 61 and Marciniec, B.; Majchrzak, M. Inorg. Chem. Commun. 2000, 3, 371). The use of Fe3 (CO) i2 has also been found to exhibit dehydrogenation silylation in the reaction of Et2 SiH and styrene. (Kakiuchi, F.; Tanaka, Y .; Chatani, N.; Murai, S. J, Organomet. Chem. 1993, 456, 45). Similarly, several cyclopentadiene iron complexes have been used to varying degrees of success, with the work of Nakazawa et al. showing interesting hydrogenation / silylation with intramolecular dehydrogenation when used with 1,3-divinyl disiloxanes. (Roman N. Naumov, Masumi Itazaki, Masahiro Kamitani, and Hiroshi Nakazawa, Journal of the American Chemical Society, 2012, Volume 134, Topic 2, pages 804-807).

A rhodium complex has been found to give low to moderate yields of allyl silanes and vinyl silanes. (Doyle, M.P .; Devora G.A.; Nevadov, A.O.; High, K.G. Organometallics, 1992, 11, 540-555). An iridium complex has also been found to give vinyl silanes in good yields. (Falck, J. R.; Lu, B, J. Org. Chem, 2010, 75, 1701-1705). Allyl silanes can be prepared in high yields using a rhodium complex (Mitsudo, T.; Watanabe, Y .; Hori, Y. Bull. Chem. Soc. Jpn. 1988, 61, 3011-3013). Vinyl silanes may be prepared by use of a rhodium catalyst (Murai, S.; Kakiuchi, F.; Nogami, K.; Chatani, N.; Seki, Y. Organometallics, 1993, 22, 4748-4750). Dehydrogenation silylation has been found to occur when complex iridium complexes were used (Oro, LA; Fernandez, MJ; Esteruelas, A. ;; Jiminez, MSJ Mol. Catalysis, 1986, 37, 151-156 and Oro, LA Fernandez, MJ;

Esteruelas, Μ. THE.; Jiminez, M.S. Organometallics, 1986, 5, 1519-1520). Vinyl silanes can also be produced using a ruthenium catalyst (Murai, S.; Seki, Y.; Takeshita, K.; Kawamoto, K.; Sonoda, NJ. Org. Chem. 1986, 51, 3890-3895) .

A palladium-catalyzed silyl Heck reaction has recently been reported to result in the formation of allyl silanes and vinyl silanes (McAtee JR, et al., Angewandte Chemie, International Edition (March 1, 2012)). U.S. Patent No. 5,955,555 discloses the synthesis of certain cobalt or iron diimine pyridine diion anion complexes. Preferred anions are chloride, bromide and tetrafluoro borate. U.S. Patent No. 7,442,819 discloses iron and cobalt complexes of certain tricyclic linkers containing a "pyridine" ring substituted with two imino groups. U.S. Patent Nos. 6,461,994, 6,657,026 and 7,148,304 disclose various catalytic systems containing certain PDI / transition metal complexes. U.S. Patent No. 7,053,020 discloses a catalytic system containing, among others, one or more bis aryl imino pyridine iron or cobalt catalysts. However, the catalysts and catalytic systems disclosed in this reference are described for use in the context of olefin oligomerizations and / or polymerizations, not in the context of dehydrogenation silylation reactions. There is a continuing need in the silylation industry for non-precious metal based catalysts that are effective for efficiently and selectively catalyzing dehydrogenation silylations. The present invention provides an answer to that need.

Summary of the Invention In one aspect, the present invention relates to a process for producing a dehydrogenation silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least at least one silyl hydride functional group, and (c) a catalyst, optionally in the presence of a solvent, to produce the silylated product by dehydrogenation, the catalyst being a Formula (I) complex or adduct thereof; (Formula I) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C6 alkyl, substituted C1 -C6 alkyl, aryl, substituted aryl, or an inert substituent, wherein R1- R5, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 3 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, where R 6 and R 7 optionally contain at least one heteroatom; optionally any two of vicinal R1, R2, R3, R4, R5, R6 and R7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and L is hydrogen, allyl, benzyl, S1R3, hydroxyl or a C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl or substituted aryl, where R is an alkyl, aryl or siloxanyl group and L optionally contains at least one heteroatom.

In another aspect, the present invention relates to a compound of Formula (II) (Formula II) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C8 alkyl, C1-4 alkyl. Substituted C 18, aryl or substituted aryl, or an inert substituent, wherein R1-R5, other than hydrogen, optionally contains at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 8 alkyl, substituted C 1 -C 18 alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure.

In another aspect, the present invention relates to a process for producing a dehydrogenation silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one group silyl hydride functional, and (c) a catalyst, optionally in the presence of a solvent, to produce the silylated product by dehydrogenation, the catalyst being a complex of Formula (III) or adduct thereof; (Formula III) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, Οχ-Cys alkyl, substituted C1-Cys alkyl, aryl, substituted aryl, or a 1 1 "Π ϊ Π P i nprfp cionHri απρ Η f 'fpTPTVhpc' from O LA -LA w L-I— 1— LA li L JL X 1 VI- VI-f O v- »XX VA VA VA LA vt> i \ X \ f VA The Va V-hydrogen optionally contain at least one heteroatom, each occurrence of R 6 and R 7 is independently C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl wherein R 6 and R 7 optionally contain at least one heteroatom, optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; L is an anionic binder selected from the group consisting of hydrogen, allyl, benzyl, SiR3, hydroxyl, or a C1 -C8 alkyl, substituted C1 -C1 alkyl, aryl or aryl group. substituted, wherein R is an alkyl, aryl, or siloxanyl group and L optionally contains at least one heteroatom; Y is a neutral binder; and Q is a non-coordinating anion.

In another aspect, the present invention relates to a process for producing a crosslinked material comprising reacting a mixture comprising (a) a silyl hydride-containing polymer, (b) a monounsaturated olefin or an unsaturated polyolefin, or combinations thereof and (c a catalyst, optionally in the presence of a solvent, to produce the crosslinked material, the catalyst being a complex of Formula (I) or adduct thereof; (Formula I) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C6 alkyl, substituted C1 -C10 alkyl, aryl, substituted aryl, or an inert substituent, wherein R1- R5, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, where R 6 and R 7 optionally contain at least one heteroatom; Ί O / 1 Cl C-k ç? optionally any two of the vicinal R, R, R, R, R, R and R together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and L is hydrogen, allyl, benzyl, SiR3, hydroxyl or a C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl or substituted aryl group, where R is an alkyl, aryl or siloxanyl group and L optionally contains at least one heteroatom.

DETAILED DESCRIPTION OF THE INVENTION The invention relates to cobalt complexes containing pyridine diimine linkers and their use as efficient dehydrogenation crosslinking and silylation catalysts. In one embodiment of the invention there is provided a complex of the Formulas (I), (II), or (III) illustrated above, wherein Co in any valence or oxidation state (e.g., +1, +2, or + 3) for use in said dehydrogenation and crosslinking silylation reactions. In particular, according to an embodiment of the invention, it has been found that a class of cobalt pyridine diimine complexes is capable of dehydrogenation silylation reactions.

Here, the term "alkyl means to include normal, branched and cyclic chain alkyl groups. Specific and non-limiting examples of alkyl include, but are not limited to methyl, ethyl, propyl and isobutyl.

Here, "substituted alkyl" means an alkyl group containing one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially or detrimentally interfere with the process.

Here "aryl" means a non-limiting group of any aromatic hydrocarbon from which a hydrogen atom has been removed. An aryl group may have one or more aromatic rings, which may be fused together by simple bonds or by other groups. Specific and non-limiting examples of aryls include, but are not limited to tolyl, xylyl, phenyl and naphthalenyl.

Here "substituted aryl" means an aromatic group as shown in the above definition of "substituted alkyl". Similar to an aryl group, a substituted aryl group may have one or more aromatic rings, which may be fused, connected by simple bonds or by other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group may be on a heteroaromatic ring (such as nitrogen) rather than on a carbon. Unless otherwise stated, it is preferred that substituted aryl groups contain from about 30 carbon atoms herein.

Here, "alkenyl" means any normal, branched or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the substitution point may be any of the double bond carbons or elsewhere in the group. Specific and non-limiting examples of alkenyls include, but are not limited to, vinyl, propenyl, allyl, metalyl, ethylidenyl norbornane.

Here, "alkynyl" means any normal, branched or cyclic alkynyl group containing one or more triple carbon-carbon bonds, where the substitution point may be any of the triple bond carbons or elsewhere in the group.

Here, "unsaturated" means one or more double or triple bonds. In one embodiment, the term "unsaturated" refers to double or triple carbon-carbon bonds. Here, the term "inert substituent" means a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the group-containing compound is subjected. Also, inert substituents do not substantially or detrimentally interfere with any process described herein wherein the compound to which they are present takes part. Examples of inert substituents include halo (fluorine, chlorine, bromine, and iodine), ether such as -OR 30 wherein R 30 is hydrocarbyl or substituted hydrocarbyl.

Here, "heteroatom" means any of the elements of Groups 13-17 except carbon, and may include, for example, oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.

Here, "olefin" means any aliphatic or aromatic hydrocarbon also containing one or more carbon-carbon aliphatic unsaturation. Such olefins may be linear, branched or cyclic and may be substituted with heteroatoms as described above, provided that the substituents do not substantially or detrimentally interfere with the desired reaction course to produce the dehydrogenated silylated product. In one embodiment, the unsaturated compound useful as a reagent in dehydrogenation silylation is an organic compound having the structural group, R2C = C-CHR, where R is an organic fragment or hydrogen.

As indicated above, the present invention relates to a process for producing a dehydrogenation silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least a silyl hydride functional group, and (c) a catalyst, optionally in the presence of a solvent, to produce the silylated product by dehydrogenation, the catalyst being a Formula (I) complex or adduct thereof; (Formula I) wherein each occurrence of R 1, R 2, R 3, R 4, and R 5 is independently hydrogen, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1 -. R5, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and L is hydrogen, allyl, benzyl, SiR 3, hydroxyl or a C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, where R is an alkyl, aryl, or siloxanyl group and L optionally contains at least one heteroatom. The catalyst used in the process of the present invention is illustrated in Formula (I) above wherein the Co is in any valence or oxidation state (e.g. +1, + 2, or +3). In one embodiment, at least one of R 6 and R 7 is wherein each occurrence of R 8, R 9, R 10, R 11, and R 12 is independently hydrogen, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl, substituted aryl, or an inert substituent, wherein R8-R12, other than hydrogen, optionally contains at least one heteroatom. R 8 and R 12 may further independently include methyl, ethyl or isopropyl groups and R 10 may be hydrogen or methyl. In a particularly preferred embodiment R 8, R 10, and R 12 may be methyl; R 1 and R 5 may independently be methyl or phenyl groups; and R2, R3 and R4 may be hydrogen. In one embodiment, the catalyst is MeB (C6F5) 3 'or tetrakis (perfluoro aryl) borate salt of the Formula (III) complex. A particularly preferred embodiment of the catalyst of the process of the present invention is the compound of Formula (II) (Formula II) wherein each occurrence of R 1, R 2, R 3, R 4, and R 5 is independently hydrogen, C 1 -C 8 alkyl, C 1-4 alkyl. Substituted C1-C18, substituted aryl or aryl, or an inert substituent, wherein R1-R5, other than hydrogen, optionally contains at least one heteroatom; each occurrence of R6 and R7 is independently C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl or substituted aryl, where R6 and R7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure.

In an alternative embodiment, the catalyst used in the process of the present invention may be in the form of Formula (III) or an adduct thereof; (Formula III) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C8 alkyl, substituted C1 -C18 alkyl, aryl, substituted aryl, or an inert substituent, wherein R1- R5, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 6 alkyl, substituted C 1 -C 18 alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and L is an anionic binder selected from the group consisting of hydrogen, allyl, benzyl, SiR3, hydroxyl, or a C1 -C6 alkyl, substituted C1 -C6 alkyl, aryl or substituted aryl, where R is an alkyl group, aryl, or siloxanyl and L optionally contains at least one heteroatom; Y is a neutral binder; and Q is a non-coordinating anion.

As defined herein, the phrase "neutral binder" means any binder without a charge. The phrase "non-coordinating anion" means an anion that interact only weakly with cations. Examples of non-coordinating anions Q include, but are not limited to [B [3,5- (CF3) 2C6H3] 4], B (C6F5) 4-, Al (OC (CF3) 3) 4 ~, and CBnH12- . Examples of neutral Y binders include dinitrogen (N2), phosphines, CO, nitrosyls, olefins, amines, and ethers. Specific examples of Y include, but are not limited to PH3, PMe3, CO, NO, ethylene, THF, and NH3.

Other preferred embodiments of the process catalysts of the invention include catalysts having the structures of Formula IV where L is an allyl group, Formula (V) where L is a benzyl group, Formula (VI) where L is SiR3 wherein R is a group alkyl, aryl, or siloxanyl, and Formula (VII) where L is hydrogen, or an adduct thereof: (Formula IV) (Formula V) (Formula VI) (Formula VII) To prepare the catalyst used in the process of the present invention may be various methods may be used. In one embodiment, the catalyst is generated at the site by contacting a catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of: a solvent, silyl hydride, the compound containing at least one unsaturated group , and combinations thereof, wherein the catalyst precursor is represented by Structural Formula (VIII) (Formula VIII) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C6 alkyl, alkyl substituted C1-C18, aryl, substituted aryl, or an inert substituent, wherein R 1-4, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 18 alkyl, substituted C 1 -C 8 alkyl, aryl or substituted aryl, where R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and X is an anion selected from the group consisting of F ”, Cl-, Br”, I ”, CF3R40SO3“ or R50COO-, where R40 is a covalent bond or a C1 -C6 alkylene group, and R50 is a hydrocarbyl group of C1 -C10. The activator may be a reducing agent or alkylating agent NaHBEt3, CH3Li, DIBAL-H, LiHMDS, as well as combinations thereof. Preferably, the reducing agent has a more negative reduction potential than -0.6 V (against ferrocene as described in Chem. Rev. 1996, 196, 877-910. A larger negative number represents a greater reduction potential). Preferably, the reduction potential ranges from -0.76 V to -2.71 V. Most preferred reducing agents have a reduction potential in the range of -2.8 to -3.1 V.

Methods for preparing catalysts are known to one of ordinary skill in the field. For example, catalysts may be prepared by reacting a PDI binder with a metal halide, such as FeBr2 disclosed in U.S. Patent Application Publication No. 2001 / 0009573A1. Typically, PDI ligands are produced by condensing an appropriate amine or aniline with 2,6-diacetyl pyridine and derivatives thereof. If desired, PDI binders may be further modified by known aromatic substitution chemistry.

In the process of the invention, catalysts may not be supported or immobilized on a support material, for example carbon, silica, alumina, MgCl2 or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, poly (amino styrene), or sulfonated polystyrene. Metal complexes may also be supported by dendrimers.

In some embodiments, for the purpose of attaching the metal complexes of the invention to a support, it is desirable that at least one of R 1 to R 9 of the metal complexes, preferably R 6, has a functional group that is effective to covalently bond to the support. Exemplary functional groups include, but are not limited to, SH, COOH, NH2, or OH groups.

In one embodiment, a silica-supported catalyst may be prepared via ring-opening metathesis polymerization (ROMP) technology discussed in the literature, for example, Macromol. Chem. Phys. 2001, 202, No. 5, pages 645-653; Journal of Chromatography A, 1025 (2003) 65-71.

One way to immobilize catalysts on the surface of dendrimers is by reaction of original Si-Cl-linked dendrimers and functionalized PDI in the presence of a base as illustrated by Kim et al. in Journal of Organometallic Chemistry 673 (2003) 77-83. The unsaturated compound containing at least one unsaturated functional group used in the process of the invention may be a compound having one, two, three or more unsaturation. Examples of such unsaturated compounds include an olefin, cycloalkene, unsaturated polyethers such as an alkyl-capped allyl polyether, a vinyl-functional alkyl-capped allyl or polyethylene, a terminally unsaturated alkyl-unsaturated amine, a terminally unsaturated alkyne, acrylate or methacrylate , unsaturated aryl ether, vinyl-functional polymer or oligomer, vinyl-functional silane, vinyl-functional silicone, unsaturated fatty acids, unsaturated esters, and combinations thereof.

Suitable unsaturated polyethers for the dehydrogenation silylation reaction are polyoxyalkylenes having the general formula: R1 (OCH2CH2) z (OCH2CHR3) w-OR2 (Formula IX) or r2o (chr3ch2o) w (ch2ch2o) z-cr42-c = c- cr42- (och2ch2) z (OCH2CHR3) WR2 (Formula X) or H2C = CR4CH20 (CH2OCH2) z (CH2OCHR3) wCH2CR4 = CH2 (Formula XI) wherein R1 represents an unsaturated organic group containing from 2 to 10 carbon atoms such as allyl, methyl allyl, propargyl or 3-pentinyl. When unsaturation is olefinic, it is desirably terminal for facilitating easy hydrogenation silylation. However, when unsaturation is a triple bond, it can be internal. R2 is hydrogen, vinyl, or a polyether capping group of 1 to 8 carbon atoms such as alkyl groups: CH3, C4H9, δ-04 -9 or i-C8Hi7, acyl groups such as CH3COO, t-C4H9COO, beta group -ketoester such as CH 3 C (O) CH 2 C (O) 0, or a trialkyl silyl group. R3 and R4 are monovalent hydrocarbon groups such as C1-C20 alkyl groups, for example methyl, ethyl, isopropyl, 2-ethylhexyl, dodecyl and stearyl, or aryl groups, for example phenyl and naphthyl, or alkaryl groups or aralkyl, for example benzyl, phenyl ethyl and nonyl phenyl, or cycloalkyl groups, for example cyclohexyl and cyclooctyl. R4 may also be hydrogen. Methyl is the most preferred group to be the groups R3 and R4. Each -y ~ d -1 · -% / - "ί d Γ7 d (1 3 ΊμΜ 1 nrl ΠΟ 1 OU d Ai d AA \ Ύ 'Ύ' d Π p 1 2 dww U 1- JL. C11 d * * d * Cl wu vd Cl J. U v —1 * J. <1 d * Id O d * v C vC w CL d Cl ddd -L. -L- di. X v-. d-. Cd d dw is 0 to 100 inclusive Preferred values of zew are 1 to 50 inclusive.

Specific examples of preferred unsaturated compounds useful in the process of the present invention include N, N-dimethyl allylamine, allyloxy, propylene, 1-butene, 1-hexene, styrene, vinyl norbornane, 5-vinyl norbornene, alpha-olefins substituted polyethers long chain linears such as 1-octadecene, internal olefins such as cyclopentene, cyclohexene, norbornene, and 3-hexene, branched olefins such as isobutylene and 3-methyl-1-octene, unsaturated polyolefins, for example polybutadiene, polyisoprene and EPDM, unsaturated esters or acids such as oleic acid, linoleic acid and methyl oleate, a vinyl siloxane of Formula (XII) and combinations thereof, wherein Formula (XII) is (Formula XII) in which each occurrence of R8 is independently C1 -C8 alkyl, substituted C1 -C8 alkyl, vinyl, aryl, and n is greater than or equal to zero.

As defined herein, "internal olefin" means an olefinic group not located at a chain termination or branch, such as 3-hexene. The silyl hydride employed in the reaction is not particularly limited. It can be any compound selected from the group consisting of RaSiH4-a, (R0) aSiH4_a, QuTvTpHDwDHxMHyMz, and combinations thereof. When used herein, each occurrence of R is independently C1 -C6 alkyl, substituted C1 -C6 alkyl, where R optionally contains at least one heteroatom, each occurrence of "a" independently has a value of 1 to 3 each of p, u, v, y and z independently have a value from 0 to 20, w and x are from 0 to 500, as long as p + x = 1 to 500 and the valencies of all elements in the silyl hydride are satisfied. Preferably, p, u, v, y and z are from 0 to 10, w and x are from 0 to 100, with p + x + y = 1 to 100.

When used herein, a group "M" represents a monofunctional group of formula R'3SiO1 / 2, a group "D" represents a bifunctional group of formula R'2SiO2 / 21 a group "T" represents a trifunctional group of formula R 'SiO3 / 2, and a group' Q 'represents a tetrafunctional group of formula Si04 / 2, a group' MH // represents HR ', 2SiO1 / 2,' Th 'represents HSIIO3 / 2, and a group' DH 'represents When used herein, g is an integer from 1 to 3. Each occurrence of R 'is independently C1 -C6 alkyl, substituted C1 -C10 alkyl, where R' optionally contains at least one heteroatom. .

Examples of silyl hydrides containing at least one silyl hydride functional group include RaSiH4_a, (RO) aSiH4_a, HSIR (OR) 3-a, R3 Si (CH2) f (SIR20) kSIRR2H, (RO) 3Si (CH2) f (SiR20 ) kSiR2H, QuTvTpHDwDHxMHyMz, and combinations thereof, where Q is SiO4 / 2, T is R 'Si03 / 2, TH is HS1O3 / 2, D is R'2Si02 / 2, DH is R'HSi02 / 2 / MH is HR 4 SiO 4, M is R 1 3 SiO 1/2, each occurrence of R and R 'is independently C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl, or substituted aryl, where R and R' optionally contain at least one heteroatom, each occurrence of a independently has a value from 1 to 3, f has a value from 1 to 8, k has a value from 1 to 11, g has a value from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 1000, x is from 0 to 1000, y is from 0 to 20, and z is from 0 to 20, as long as p + x + y is equal to ala 3000, the valencies of all elements in the silyl hydride are satisfied. In the above formulations, p, u, v, y, and z may also be from 0 to 10, w and x may be from 0 to 10 0, where p + x + y is equal to ala 100.

In one embodiment, the silyl hydride has one of the following structures: R1a (R20) bSiH (Formula IX) - - (Formula X), (Formula XI), or (Formula XII) wherein each occurrence of R1, R2, R3 , R 4, and R 5 are independently C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, R 6 is hydrogen, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, and x and y are independently greater than or equal to 0 (x is at least 1 in Formula X), and ea and b are integers from 0 to 3 with a + b = 3.

The catalysts shown in Formulas (I, II and III) are useful for catalyzing dehydrogenation silylation reactions. For example, when a suitable silyl hydride such as triethoxy silane, triethyl silane, MDhM, or a silyl hydride-functional polysiloxane (SL 6020 from Momentive Performance Materials, Inc., for example) reacts with a monounsaturated hydrocarbon such as octene, dodecene, butene, etc., in the presence of a Co catalyst, the resulting product is a terminally silyl substituted alkene, where the unsaturation is in a beta position relative to the silyl group. A byproduct of this reaction is hydrogenated olefin. When the reaction is carried out with a silane to olefin molar ratio of 0.5: 1, the resulting products are formed in a 1: 1 ratio. The reaction scheme below shows an example.

Typically, reactions are easy at ambient temperatures and pressures, but can also occur at higher or lower temperatures (0 to 300 ° C) and pressures (ambient at 3000 psi). In this reaction, a range of unsaturated compounds such as Ν, Ν-dimethyl allylamine, allyloxy substituted polyethers, cyclohexene, and linear alpha-olefins (i.e. 1-butene, 1-octene, 1 dodecene, etc.). When an alkene containing double internal bonds is used, the catalyst is capable of isomerizing olefin, with the resulting reaction product being the same as when using terminal unsaturated alkene.

If the reaction occurs with a silyl hydride to olefin ratio of 1: 1, where the silyl groups are in terminal positions of the compound and there is still an unsaturated group present in the product.

If the catalyst is first used to prepare a terminally substituted alkenylsilyl, a second silane may be added to produce an asymmetrically substituted bisilylene. The resulting silane is terminally substituted at both ends. This bis silane may be a useful starting material for the production of omega-substituted alpha alkanes or alkenes such as diols and other compounds readily derived from the silylated product. Today, omega-substituted alpha alkanes or alkenes are not readily prepared, and may have a variety of uses for preparing single polymers (such as polyurethanes) or other useful compounds.

Since the double bond of an alkene is preserved during the hydrogenation silylation reaction employing these cobalt catalysts, a monounsaturated olefin can be used to crosslink silyl hydride-containing polymers. For example, a silyl hydride polysiloxane, such as SL6020 (MDisDH3oM), may react with 1-octene in the presence of the cobalt catalysts of this invention to produce a crosslinked elastomeric material. By this method, a variety of new materials can be produced by varying the hydride polymer and the length of the olefin used for crosslinking. Accordingly, the catalysts used in the process of the invention have utility in the preparation of useful silicone products, including, but not limited to coatings, for example release coatings, room temperature vulcanisates, sealants, adhesives, agricultural products and applications. personal care, and silicone surfactants to stabilize polyurethane foams.

In addition, dehydrogenation silylation may be performed on any of a number of unsaturated polyolefins, such as polybutadiene, polyisoprene or EPDM-like copolymer, either to functionalize these commercially important polymers with silyl groups or to crosslink them via use. of hydrosiloxanes containing multiple SiH groups at temperatures lower than those conventionally used. This offers the potential to extend the application of these already valuable materials to newer commercially useful areas.

In one embodiment, the catalysts are useful for dehydrogenation silylation of a composition containing a silyl hydride and a compound having at least one unsaturated group. The process includes contacting the composition with a metal catalyst complex, whether supported or unsupported, to cause the silyl hydride to react with the compound having at least one unsaturated group to produce a dehydrogenation silyl product, which may contain the metal complex catalyst. Optionally, the dehydrogenation silylation reaction may be performed in the presence of a solvent. If desired, when the dehydrogenation silylation reaction is completed, the metal complex may be removed from the reaction product by magnetic separation and / or filtration. These reactions may be performed pure, or diluted in an appropriate solvent. Typical solvents include benzene, toluene, diethyl ether, etc. It is preferred to perform the reaction in an inert atmosphere. The catalyst can be generated at the site by reduction using an appropriate reducing agent.

The catalyst complexes of the invention are efficient and selective for catalyzing dehydrogenation silylation reactions. For example, when the catalytic complexes of the invention are employed in the dehydrogenation silylation reaction of an alkyl capped allyl polyether or a compound containing an unsaturated group, the reaction products are essentially free of unreacted alkyl capped allyl polyether and its isomerization products. In one embodiment, the reaction products do not contain the unreacted alkyl capped allyl polyether and its isomerization products. In addition, when the compound containing an unsaturated group is an unsaturated amine, the dehydrogenated silylated product is essentially free of inorganic addition products and unsaturated amine isomerization products. When used herein, "essentially free" means no more than 10 wt%, preferably 5 wt% based on the total weight of the hydrosilylation product. "Essentially free from internal addition products" means that silicon is added to the terminal carbon.

The following examples are intended to illustrate but not to limit the scope of the present invention. All parts and percentages are by weight and all temperatures are in degrees Celsius unless stated otherwise. All publications and US patents referred to in this application are incorporated entirely by reference.

Examples General Considerations All moisture and air sensitive manipulations were performed using standard Schlenk vacuum line and cannula techniques or in an MBraun inert atmosphere dry box containing a pure nitrogen atmosphere. Solvents for moisture and air sensitive manipulations were initially dried and deoxygenated using literature procedures (Pangborn, A.B. et al., Organometallics 15: 1518 (1996)). Chloroform-d and benzene-d6 were purchased from Cambridge Isotope Laboratories. (1PrPDI) C0N2 complexes, (Bowman AC et al., JACS 132: 1676 (2010)), (EtPDI) CoN2, (Bowman AC et al., JACS 132: 1676 (2010)), (iPrBPDI) CoN2, ( Bowman AC et al., JACS 132: 1676 (2010)), <MesPDI) CoCH3 (Humphries, MJ

Organometallics 24: 2039.2 (2005)), (MesPDI) CoCl, (Humphries, MJ Organometallics 24: 2039.2 (2005)) [(MesPDI) CoN2] [MeB (C6F5) 3] (Gibson, VC et al., J. Chem. Comm. 2252 (2001)), and [(MesPDI) COCH3] [BArF24] (Atienza, CCH et al., Angew. Chem. Int. Ed. 50: 8143 (2011)) were prepared according to literature procedures. reported. Bis (trimethyl siloxy) methyl silane (MD'M), (EtO) 3SiH and Et3SiH were purchased from Momentive Performance Materials and were distilled from calcium hydride before use. The substrates, 1-octene (TCI America), tertiary butylene or TBE (Alfa Aesar), N, N-dimethyl allylamine (TCI America) and styrene (Alfa Aesar) were dried on calcium hydride and distilled off under reduced pressure. use. 1-Butene (TCI America), allylamine (Alfa Aesar) and allyl isocyanate (Alfa Aesar) were dried in 4Â ° molecular sieves. SilForce® SL6100 (MviDi20Mvi), SilForce® SL6020 (MDi5Dh30M) and allyl polyethers were purchased from Momentive Performance Materials and dried under high vacuum for 12 hours before use.

1H NMR spectra were recorded on Inova 400 and 500 spectrometers operating at 399.78 MHz and 500.62 MHz, respectively. 13 C NMR spectra were recorded on an Inova 500 spectrometer operating at 125, 8 93 MHz. All XH and 13 C NMR chemical shifts were reported relative to SiMe4 using the 1 H (residual) and 13 C chemical shifts of the 1 H NMR. solvent as a secondary standard. The following abbreviations and terms are used: broad singlet; singlet; triplet; bm- broad multiplet; GC-gas chromatography; MS- mass spectroscopy; THF-tetrahydrofuran.

GC analyzes were performed using a Shimadzu GC-2010 gas chromatograph equipped with a Shimadzu AOC-20s automatic feed system and a Shimadzu SHRXI-5MS capillary column (15 mx 250 pm). The instrument was set to an injection volume of 1 μΐ ,, · an input split ratio of 20: 1, an input temperature of 250 ° C and a detector temperature of 275 ° C. UHP grade helium was used as a carrier gas with a flow rate of 1.82 mL / min. The temperature program used in all analyzes is as follows: 60 ° C, 1 min; 15 ° C / min at 250 ° C, 2 min.

Catalyst loads in the following text are reported in mole% of the cobalt complex (mole CO complex / rftOlolefin X 100).

Example 1: Synthesis of (MesPDI) CO 2. This compound was prepared similarly to the synthesis of (1PrPDI) C0N2 (Bowman, supra) with 0.500 g (0.948 mmol) of (MesPDI) C0Cl2, 0.110 g (4.75 mmol, 5.05 equiv) of sodium and 22.0 g (108 mmol, 114 equiv.) Of mercury. Recrystallization from pentane / toluene 3: 1 yielded 0.321 g (70%) of very dark emerald colored crystals identified as (MesPDI) CoN2. Analysis for C 27 H 31 N 5 CO: Calc'd C, 66.93; H 6.45; N, 14.45. Found C, 66.65; H 6.88; N, 14.59. 1H-NMR (benzene-d6): 3.58 (15 Hz), 4.92 (460 Hz). IR (benzene): δ = 2089 cm -1.

Example 2: Synthesis of (MesPDI) CoOH. A small 20mL scintillation vial was charged with 0.100 g (0.203 mmol) (MesPDI) CoCl, 0.012 g (0.30 iranol, 1.5 equiv) of NaOH, and approximately 10 mL of THF. The reaction was stirred for two days after which the color of the solution changed from dark pink to red. The THF was removed in vacuo and the residue was dissolved in approximately 20 mL of toluene. The resulting solution was filtered through Celite and the solvent removed from the filtrate in vacuo. Recrystallization of the crude pentane / toluene product 3: 1 yielded 0.087 g (90%) of dark pink crystals identified as (MesPDI) CoOH. The compound is dichroic in solution displaying pink with a green color. Analysis for C 27 H 32 CON 3 O: Calc'd C, 68.49; H 6.81; N, 8.87. Found C, 68.40; H, 7.04; N, 8.77. 1H-NMR (benzene-dg): δ = 0.26 (s, 6H, C (CH3)), 1.07 (s, 1H, CoOH), 2.10 (s, 12H, o-CH3), 2 , 16 (s, 6H, p-CH 3), 6.85 (s, 4H, m-aryl), 7.49 (d, 2H, m-pyridine), 8.78 (t, 1H, p-pyridine) . 13 C {1H} NMR (benzene di): δ = 19.13 (o-CH3), 19.42 (C (CH3)), 21.20 (p-CH3) 114.74 (p-pyridine), 121.96 (m-pyridine), 129.22 (m-aryl), 130.71 (o-aryl), 134.78 (p-aryl), 149.14 (i-aryl), 153.55 (o - pyridine), 160.78 (C = N). IR (benzene): OH = 3582 cm -1.

Example 3: Silylation of 1-ctenum with MDHM using various Co. complexes. In a dry box filled with nitrogen, a small scintillation vial of 0.100 g (0.891 mmol) of 1-octene and 0.009 mmol (1%) was charged. molar) of the cobalt complex (see Table 1 for specific amounts). Then, 0.100 g (0.449 mmol, 0.50 equiv.) Of MDHM was added to the mixture and the reaction was stirred at room temperature for one hour. The reaction was rapidly cooled by exposure to air and the product mixture was analyzed by gas chromatography and NMR spectroscopy.

Table 1. Catalyst examination for 1-octene silylation with MDHM. * *% product conversion and distribution determined by GC-FID. % octane and% silyl product reported as percentages of compounds in the reagent mixture.

Example 4: Silylation of 1-octene with different silanes using (MesPDI) C0CH3 and (MesPDI) C0N2 - In a dry nitrogen-filled box, a small scintillation vial of 0.100 g (0.891 mmol) of 1-octene and 0.009 was charged. mmol (1 mole%) of the cobalt complex [0.004 g (MesPDI) COCH3 or 0.004 g (MesPDI) CoN2]. Then, 0.449 mmol (0.5 equiv) of silane (0.100 g MDHM, 0.075 g (EtO) 3 SiH or 0.052 g Ets SiH) was added to the mixture and the reaction was stirred at room temperature for the desired time. The reaction was rapidly cooled by exposure to air and the product mixture was analyzed by gas chromatography and NMR spectroscopy. Table 2 shows the results.

Table 2. Silylation of 1-cene with various silanes. * *% Product conversion and distribution determined by GC-FID. % octane and% silyl product reported as percentages of compounds in the reagent mixture.

Example 5: Activation at the site of cobalt precatalysts. A small scintillation flask was charged with 0.100 g (0.891 mmol) of 1-octene, 0.100 g (0.449 mmol) of MDhM and 0.005 g (0.009 mmol, 1 mol%) of (MesPDI) CoCl2. Then, 0.019 mmol (2 mol%) of activator (0.019 mL 1.0 M NaHBEt3 in toluene; 0.012 mL 1.6 M CH3 Li in diethyl ether; 0.019 mL 1.0 M DIBAL-H in toluene; 0.003 g) was added. LiHMDS) in the mixture and the reaction was stirred for 1 hour at room temperature. The reaction was rapidly cooled by exposure to air followed by GC analysis of the mixture. In all cases, complete conversion of 1-octene to approximately 1: 1 mixture of 1-bis (trimethyl siloxy) methyl silyl-2-octene and octane was observed.

Example 6: Silylation of cis- and trans-4-octene with different silanes using (MesPDI) COCH3. Reactions were performed similarly to 1-octene silylation using 0.100 g (0.891 mmol) of cis- or trans-4-octene and 0.009 mmol (1 mol%) of cobalt complex (0.004 g (MesPDI) C0CH3 ), and 0.629 mmol (0.5 equiv.) of silane (0.100 g MDhM, 0.075 g (EtO) 3 SiH or 0.052 g Et3 SiH). The reactions were stirred at room temperature for 24 hours and then quenched by exposure to air and the product mixtures were analyzed by gas chromatography and NMR spectroscopy. Table 3 shows the results.

Table 3. Cis- and trans-4-octene silylation with various silanes. * *% Conversion and product distribution determined by GC-FID. % octane and% silyl product reported as percentages of compounds in the reagent mixture.

Example 7: 1-Octene silylation with MDHM using (MesPDI) CoCH3 in the presence of H2. In a dry box filled with nitrogen was charged a thin-walled glass vessel with 0.200 g (1.78 mmol) of 1-octene and 0.400 g (1.80 mmol) of MDHM. The solution was frozen in the cold well and 0.008 g (0.017 mmol, 1 mol%) of (MesPDI) COCH3 was added to the surface of the frozen solution. The reaction vessel was quickly pulled over, removed from the dry box and placed in a Dewar vessel filled with liquid nitrogen to keep the solution frozen. The vessel was degassed and approximately 1 atm H2 was admitted. The solution was thawed and stirred at room temperature for one hour. The reaction was cooled rapidly by opening the glass vessel in air. GC analysis of the product mixture showed conversion greater than 98% of 1-octene to octane (74%) and 1-bis (trimethyl siloxy) methyl silyl octane (24%).

Example 8: 1-Octene hydrosilylation with MDHM using [(MesPDI) CoN2] [MeB (C6F5) 3]. To generate [(Mespo j) coN2] [MeB (CgFi)) 3], a small 20 mL scintillation vial was charged with 0.004 g (0.008 mmol) of (MesPDI) CoCH3, 0.005 g (0 1.0 mmol, 1.2 equiv.) Of B (C6F5) 3 and approximately 2 mL of toluene. The reaction was stirred for 10 minutes followed by vacuum removal of the solvent. Then, 0.100 g (0.891 mmol) of 1-octene and 0.200 g (0.899 mmol) of MDKM were added and the reaction was stirred at room temperature for 24 hours. The reaction was rapidly cooled by exposure to air. GC analysis and 2Η NMR spectroscopy showed 90% conversion of the starting material to 1-bis (trimethyl siloxy) methyl silyl octane (68%), 1-bis (trimethyl siloxy) methyl silyl 2-octene (12% ) and octane (10%).

Product characterization: 1-bis (trimethyl siloxy) methyl silyl-2-octene. 1H NMR (benzene-d6): δ = 0.16 (s, 3H, (OTMS) 2 SiCH3), 0.18 (s, 18H, OSi (CH3) 3), 0.90 (t, 3H, Hh) 1.27 (m, 2H, Hf), 1.29 (m, 2H, Hg), 1.40 (m, 2H, He), 1.59 (d, 2H {75%}, Ha - trans isomer ), 1.66 (d, 2H {25%}, Ha - cis isomer), 2.07 (m, 2H {75%}, Hd - trans isomer), 2.11 (m, 2H {25%}, Hd - cis isomer), 5.44 (m, 1H {75%}, Hc - trans isomer), 5.48 (m, 1H {25%}, Hc - cis isomer), 5.55 (m, 1H { 75%}, Hb - trans isomer), 5.60 (m, 1H (25%}, Hb - cis isomer). 13 C {1H} NMR (benzene-dg): δ = -0.46 ((OTMS) 2 SiCH3), 2.04 (OSi (CH3) 3), 14.35 (Ch), 22.99 (Cg-trans ), 23.05 (Cg-cis), 24.12 (Cf), 29.87 (Ce-cis), 30.00 (Ce-trans), 31.79 (Cf-trans), 32.05 (Cf - cis), 33.37 (Cd), 124.37 (Cb - cis), 125.14 (Cb - trans), 129.06 (Cc - cis), 130.47 (Cc - trans). 1-triethoxy sil1-2-octene. 1H NMR (benzene-d6): δ = 0.88 (t, 3H, Hh), 1.19 (t, 9H, OCH2 CH3), 1.26 (m, 2H, Hf), 1.26 (m, 2H, Hg), 1.36 (m, 2H, He), 1.74 (d, 2H (75%}, Ha-trans isomer), 1.78 (d, 2H {25%}, Ha-cis isomer), 2.02 (m, 2H {75%}, Hd - trans isomer), 2.13 (m, 2H {25%}, Hd - cis isomer), 3.83 (q, 6H, OCH 2 CH 3) 5.45 (m, 1H {75%}, Hc - trans isomer), 5.49 (m, 1H {25%}, Hc - cis isomer), 5.66 (m, 1H {75%}, Hb - trans isomer), 5.69 ( m, 1H (25%}, Hb - cis isomer). 13 C 1 H NMR (benzene-d 6): δ = 14.35 (Ch), 17.14 (Ca), 18.61 (OCH2 CH3), 22.98 (Cg), 17.14 (Ca), 29 , 87 (Ce), 31.72 (Cf), 33.26 (Cd-trans), 33.47 (Cd-cis), 58.69 (OCH2CH3), 123.38 (Cb-cis), 124.26 (Cb - trans), 130.94 (Cc - trans), 130.98 (Cc - cis). 1-triethyl silyl-2-octene. 1H NMR (benzene-d6): δ = 0.55 (t, 6H, Si (C.H2CH3) 3), 0.91 (t, 3H, Hh), 0.97 (t, 9H, Si (CH2CH3) ) 3), 1.28 (m, 2H, tf), 1.32 (m, 2H, tf), 1.36 (m, 2H, tf), 1.50 (d, 2H {75%}, tf - trans isomer), 1.54 (d, 2H {25%}, tf - cis isomer), 2.03 (m, 2H {75%}, tf-trans isomer), 2.08 (m, 2H {25 %}, tf - cis isomer), 5.47 (m, 1H {75%}, tf - trans isomer), 5.50 (m, 1H {25%}, H ° - cis isomer), 5.36 ( m, 1H {75%}, tf - trans), 5.38 (m, 1H {25%}, tf - cis isomer). 13 C {3 H} NMR (benzene-d 6): δ = 2.82 (Si (CH 2 CH 3) 3), 7.70 (Si (CH 2 CH 3) 3), 14.42 (Ch), 17.70 (Ca - trans ), 17.71 (Ca - cis), 23.04 (Cf), 23.19 (Ce), 29.24 (Cf), 32.40 (Cf - trans), 32.41 (Cf - cis), 126.41 (C *-trans), 126.46 (cf-cis), 129.31 (Cc-trans), 129.33 (Cc-cis).

Example 9: Silylation of 1-butene with different silanes using (MesPDI) COCH3. A thin-walled glass vessel was charged with 0.459 mmol of silane (0.100 g MD'M, 0.075 g (EtO) 3 SiH or 0.052 g Et3 SiH) and 0.004 g (0.009 mmol) of (MesPDI) CoCH3. The mixture was frozen in liquid nitrogen and the vessel degassed. 0.891 mmol of 1-butene was introduced into the vessel using a calibrated gas bulb. The mixture was thawed and stirred at room temperature for 1 hour. Volatiles were distilled in a J. Young tube containing CDCl3 and analyzed by NMR spectroscopy. The remaining residue was exposed to air and analyzed by GC and NMR spectroscopy. Table 4 shows the results.

Table 4. Silylation of 1-butene with various silanes. * *% Conversion and distribution of products as determined by GC and 1 H NMR spectroscopy.

Product characterization: 1-bis (trimethyl siloxy) methyl silyl-2-butene. 1H NMR (CDCl3): δ = 0.00 and 0.01 (s, 2x3H, (OTMS) 2SiCH3), 0.08 and 0.09 (s, 2x18H, OSi (CH3) 3), 1.38 and 1.45 (d, 2x2H, SiCH2 CH = CH), 1.57 and 1.64 (d, 2x3H, CH = CHCH3), 5.25 to 5.43 (m, 4x1H, CH = CH). 13 C NMR (δH) (CDCl3): δ = -0.44 and -0.60 ((OTMS) 2SCH3); 1.98 (OSi (CH 3) 3); 18.27 (CH = CHCH3); 19.19 and 23.71 (SiCH2 CH = CH); 122.17, 124.12, 125.34, 126.09 (CH = CH). 1-triethoxy silyl-2-butene. 1H NMR (CDCl3): δ = 1.21 (t, 2x9H, OCH2 Cl3), 1.55 and 1.60 (d, 2x2H, SiCH2 CH = CH), 1.61 and 1.62 (d, 2x3H, CH = CHCl3), 3.81 and 3.82 (q, 2x6H, OCH2 CR3), 5.38 to 5.48 (m, 4x1H, CH = CH). 13 C NMR (XH) (CDCl3): δ = II.84 (SiCH2 CH = CH); 18.20 and 18.23 (CH = CHCH3); 18.36 and 18.38 (OCH2 CH3); 58, 64 and 58.65 (OCH 2 CH 3); 123, 33, 123, 68, 124.46, 125.31 (CH = CH).

Example 10: MDHM TBE silylation using (MesPDI) CoCH3. This reaction was performed similarly to 1-butene silylation using 0.100 g (0.449 mmol) of MDHM, 0.004 g (0.009 mmol) of (Mespoi) coCH3 and 0.891 mmol of TBE. Volatile analysis by 1N NMR spectroscopy showed a 4: 1 mixture of unreacted TBE and 2,2-dimethyl butane (33% conversion). Analysis of the product silane by GC and NMR spectroscopy showed only trans -1-bis (trimethyl siloxy) methyl silyl-3,3-dimethyl-1-butene. 1H NMR (CDCl3): δ = 0.00 (s, 3H, (0TMS) 2 SiCH3), 0.09 (s, 18H, OSi (C13 H13) 3), 0.99 (s, 9H, C (CH3) 3), 5.37 (d, J = 19.07, 1H SiCH = CH), 6.13 (d, J = 19.07 Hz, 1H, CH = C 17 C (CH 3) 3). 13 C NMR (XH} (CDCl3): δ = 0.00 ((OTMS) 2S1CH3); 2.01 (OSi (CH3) 3); 28.96 (C (CH 3) 3); 34.91 (C (CH 3) 3); 121.01 (SiCH = CH); 159.23 (SiCH = CH). Example 11: Silylation of Δ, Ν-dimethyl allylamine with different silanes using (MesPDI) C0CH3 and (MesPDI) CoN2. In a dry box filled with nitrogen, a small scintillation vial containing 0.090 g (1.1 mmol) of N, N-dimethyl allylamine and 0.5 mmol (0.5 equiv) of silane (0.118 g of MDHM, 0.087 g (EtO) 3 SiH or 0.062 g of Et 3 SiH). Then 0.01 mmol (1 mol%) of cobalt complex [0.005 g (MesPDI) COCH3 or 0.005 g (MesPDI) CoN2] was added and the reaction was stirred for one hour at room temperature. The reaction was rapidly cooled by exposure to air and the product mixture was analyzed by NMR spectroscopy. Table 5 shows the results.

Table 5. Silylation of α, β-dimethyl allylamine with various silanes. * *% Product conversion and distribution determined by XH NMR spectroscopy.

Product characterization: N, W-dimethyl-3-bis (trimethyl siloxy) methyl silyl-1-propenyl amine. 1 H-NMR (benzene-d #): δ = 0.14 (s, 3H, (OTMS) 2 SiCH3), 0.18 (s, 18H, OSi (CÜ3) 3) δ 1/50 (dd, J = 7, 7.2 Hz, 2H, SiCH2 CH = CH), 2.35 (s, 6H, N (C13 H2) 2), 4.25 (dt, J = 13.6, 7.7 Hz, 1H, CH 2 Cl = 1). CH), 5.80 (dt, J = 13.6, 1.2 Hz, 1H, CH 2 CH = CH). 13 C {1H} NMR (benzene-d6 ·): δ = 0.61 ((OTMS) 2 SiCH3), 2.12 (OSi (CH3) 3) / 20.49 (SiCH2CH = CH), 41.08 (N (CH 3) 2) / 94.09 (CH 2 CH = CH), 140.57 (CH 2 CH = CH). N, N-dimethyl-3-triethoxy silyl-1-propenyl amine. 1H-NMR (benzene-dg): δ = 1.18 (t, J = 7.0, 9H, OCH2 CH3), 1.66 (dd, J = 7.5, 1.2 Hz, 2H, SiCi72CH = CH ), 2.30 (s, 6H, N (CH 5) 2), 3.84 (q, J = 7.0, 6H, OC 17 CH 3), 4.31 (dt, J = 13.6, 7.5 Hz , 1H, CH 2 CH = CH), 5.85 (dt, J = 13.6, 1.2 Hz, 1H, CH 2 CH = CH). 13 C NMR (benzene d 6): δ = 13.48 (SiCH 2 CH = CH), 18.41 (OCH 2 CH 3), 40.98 (N (CH 3) 2), 58.65 (OCH 2 CH 3), 92.95 (CH 2 CH = CH), 140.82 (CH 2 CH = CH).

Example 12: Silylation of methyl capped allyl polyether (H2C = CHCH20 (C2H40) 8.9CH3) with methyl bis (trimethyl silyloxy) silane (MDHM). A small scintillation vial containing 0.100 g of methyl capped allyl polyether having an average formula H2C = CHCH20 (C2H40) 3.9CH3 (0.215 mmol) and 0.025 g (0.11 mmol, 0.5 equiv) of Μϋ'Μϋ was charged. .

To the stirred solution of polyether silane was added 1 mg (0.002 mmol, 1 mol%) of (MesPDI) COCH3. The small scintillation vial was sealed and removed from the dry box and placed in an oil bath at 65 ° C. The reaction mixture was stirred for 1 hour after which the small vial was removed from the oil bath and the reaction rapidly cooled by opening the vessel in air. XH NMR spectrum analysis of the product established a 1: 1 mixture of silylated product and propyl polyester. (OTMS) 2 Si (CH 3) CH 2 CH = CHO (C 2 H 4 O) 8.9 CH 3. 1H-NMR (CDCl3): δ = -0.06 (s, 3H, (OTMS) 2 SiCl), 0.03 (s, 18H, OSi (CH3) 3), 1.55 (dd, J = 7.8 1.1 Hz, 2H, SiCif 2 CH = CH), 3.32 (s, 3H, 00¾), 3.5-3.7 (O-CH 2 CH 2 -O), 5.28 (dt, J = 18.5 1.1 Hz, 1H, CH 2 CH = C 1), 6.07 (dt, J = 18.5, 7,8 Hz, 1H, CH 2 Cl = CH). 13 C NMR (½} (CDCl3): δ = 0.11 ((OTMS) 2 SiCH3), 1.65 (OSi (CH3) 3), 29.24 (SiCH2 CH = CH), 59.00 (0CH3), 70 -72 (O-CH 2 CH 2 O), 127.02 (CH 2 CH = CH), 144.38 (CH 2 CH = CH).

Example 13. Styrene hydrosilylation. A thin-walled glass vessel was charged with 0.5 g (4.80 mmol) styrene, 1.080 g (4.854 mmol, 1.01 equiv) MD'M and 0.020 g (0.042 mmol, 1 mol%). ) of (MesPDI) COCH3. The reaction was stirred in an oil bath at 75 ° C for 96 hours, then quenched by exposure to air. 1H NMR spectrum analysis of the product mixture showed 20% conversion of styrene to bis (trimethyl siloxy) methyl (phenyl ethyl) silane (15%), and ethyl benzene (5%). Bis (trimethyl siloxy) methyl disilane ((OTMS) 2 SiCH3] 2 was observed by GC / MS.

Example 14: Crosslinking of MvlD12oMvl (SL 6100) and MD15DH30M (SL 6020) at room temperature. A small scintillation vial was charged with 1.0 g Mv1Di2oMv: 1 (SL 6100) in which MV1 is vinyl dimethyl SiO, and 0.044 g of MDi5Dh3oM (SL 6020). In a second small vial a catalyst solution was prepared by dissolving 0.010 g of (MesPDI) COCH3 or (MesPDI) CoN2 in approximately 0.300 g of toluene. The catalyst solution was added with stirring to a SL 6100 and SL 6020 solution and the reaction was monitored for gel formation. After rapid cooling of the reaction by exposure to air the resulting gel was softer than that obtained from the same reaction using Karstedt compound as a catalyst.

Polymer crosslinking was also investigated under clean conditions by adding 0.010 g of (MesPDI) COCH3 or (MesPDI) CoN2 to a stirred solution of 1.0 g of SL 6100 and 0.044 g of SL 6020.

Example 15: Crosslinking of Mv1Di2oMv: 1 (SL 6100) and MDi5DH30M (SL 6020) at 65 ° C. These reactions were performed similarly to those performed at room temperature, with the additional steps of sealing the small scintillation vials by removing them from the dry box and placing them in an oil bath at 65 ° C. After rapid cooling of the reaction, the resulting gels were imperceptible to those obtained from the same reaction using Karstedt compound as a catalyst. Table 6 shows the results.

Table 6. Gelling time for crosslinking of SL 6100 and SL 6020 under various reaction conditions. * RT = room temperature.

Double silylation experiments Example 16: Silylation of 1-bis (trimethyl siloxy) methyl silyl-2-octene with MDHM using (MesPDI) COCH3. This experiment was performed similarly to 1-octene silylation using 0.100 g (0.301 mmol) of 1-bis (trimethyl siloxy) methyl silyl-2-octene, 0.034 g (0.152 mmol, 0.51 equiv.) Of MD M, and 0.001 g (0.002 mmol, 1 mol%) of (Mespoi) coCH 3. The reaction was stirred at room temperature for 24 hours and cooled rapidly upon exposure to air. Analysis of the mixture by GC-FID, GC-MS and NMR spectroscopy showed an approximately 1: 1 mixture of 1-bis (trimethyl siloxy) methyl silyl octane and 1,8-bis (bis (trimethyl siloxy) methyl silyl) Octene (major isomer).

Attempts to silyl 1-triethoxy silyl-2-octene with MDhM produced a mixture of disilylated products concomitantly with the formation of 1-triethoxy silyl octane. Silylation of 1-bis (trimethyl siloxy) methyl silyl-2-octene and 1-triethoxy silyl-2-octene with TES under the same conditions yielded only hydrogenated products, 1- bis (trimethyl siloxy) methyl silyl octane and 1-triethoxy silyl octane, respectively.

Example 17: Alternative procedure for 1-octene double silylation with MDHM using (MesPDI) COCH3. This experiment is performed similarly to 1-octene silylation using 0.100 g (0.891 mmol) of 1-octene, 0.150 g (0.674 mmol, 0.756 equiv) of MDHM and 0.004 g (0.008 mmol, 1 mol%). ) of (MesPDI) COCH3. The reaction was stirred at room temperature for 24 hours and cooled rapidly upon exposure to air. GC-FID mixture analysis showed a 1: 0.5: 0.5 mixture of octane, 1-bis (trimethyl siloxy) methyl silyl octane and 1,8-bis (bis (trimethyl siloxy) methyl silyl) -2- octene (major isomer), respectively.

Example 18: Silylation of 1-bis (trimethyl siloxy) methyl silyl-2-butene with MDHM using (MesPDI) COCH3. This experiment was performed similarly to the silylation of 1-bis (trimethyl siloxy) methyl silyl-2-octene using 0.100 g (0.361 mmol) of 1-bis (trimethyl siloxy) methyl silyl-2-butene, 0.040 g (0 , 18 mmol, 0.50 equiv.) MDHM and 0.002 g (0.004 mmol, 1 mol%) of (MesPDI) CoCH3. The reaction was stirred for 24 hours and cooled rapidly upon exposure to air. Analysis of the mixture by NMR spectroscopy showed the following products: 50% 1-bis (trimethyl siloxy) methyl silyl butane; 26% trans-1,4-bis (bis (trimethyl siloxy) methyl silyl) -2-butene; 17% cis-1,4-bis (bis (trimethyl siloxy) methyl silyl) -2-butene; 5% trans-1,3-bis (bis (trimethyl siloxy) methyl silyl) -1-butene; and 2% trans-1,4-bis (bis (trimethyl siloxy) methyl silyl) -1-butene.

Product characterization: 1-bis (trimethyl siloxy) methyl silyl butane. 1H NMR (CDCl3): δ = 0.01 (s, 3H, (OTMS) 2SiCH3), 0.09 (s, 18H, OSx (CH3) 3) r 0.45 (m, 2H, SYCC2CH2CH2CH3), 0 88 (t, 3H, SYCH 2 CH 2 CH 2 CH 3), 1.26-1.33 (m, 4H, SYCH 2 CH 2 CH 2 CH 3). 13 C NMR (XH} (CDCl3): δ = -0.66 ((OTMS) 2 SiCH3), 2.02 (OSi (CH3) 3), 13.98 (SYCH2 CH2 CH2 CH3), 17.46 (SYCH2 CH2 CH2 CH3), 25, 35 and 26.36 (SYCH2 CH2 CH2 CH3).

Trans-1,4-bis (bis (trimethyl siloxy) methyl silyl) -2-butene. 1H NMR (CDCl3): δ = 0.01 (s, 3H, (OTMS) 2 SiCff3), 0.09 (s, 18H, OS (C H3) 3), 1.39 (d, 4H, SiCH2 CH = CHCl 2 Si), 5.21 (t, 2H, SYCH 2 CH = CHCH 2 Si). 13 C NMR (δ} (CDCl3): δ = -0.66 ((OTMS) 2SCH 3), 2.02 (OSi (CH 3) 3), 23.95 (Si CH 2 CH = CHCH 2 Si), 124.28 (SiCH 2 CH = CHCH2 Si).

Cis-1,4-bis (bis (trimethyl siloxy) methyl silyl) -2-butene. Λη NMR (CDCl3): δ = 0.01 (s, 3H, (OTMS) 2 SiCH3), 0.09 (s, 18H, OSi (CH3) 3), 1.41 (d, 4H, S ± CH2 CH = CHCH 2 S +), 5.31 (t, 2H, SiCH 2 Cl = CHCH 2 Si). 13 C {1 H NMR (CDCl 3): δ = -0.38 ((OTMS) 2 SiCH 3), 2.01 (OSi (CH 3) 3), 19.12 (SiCH 2 CH = CHCH 2 Si), 122.86 (SiCH 2 CH = CHCH 2 Si) ).

Trans-1,3-bis (bis (trimethyl siloxy) methyl silyl) -1-butene. 3H NMR (CDCl3): δ = 0.01 (s, 3H, (OTMS) 2 SiCH3), 0.09 (s, 18H, OSi (CH3) 3), 1.04 (d, 3H, CHCH3), 1 , 64 (m, 1H, CACH 3), 5.28 (d, 1H, SiCH = CH), 6.27 (dd, 1H, SiCH = CiT). 13 C NMR (δ} (CDCl3): δ = -0.13 ((OTMS) 2 SiCH3), 2.00 (OSi (CH3) 3), 12.07 (CHCH3), 31.69 (CHCH3), 123, 37 (SiCH-CH), 151.01 (SiCH = CH).

Trans-1,4-bis (bis (trimethyl siloxy) methyl silyl) -1-butene. 1H NMR (CDCl3): δ = 0.01 (s, 3H, (OTMS) 2SiCH 3), 0.09 (s, 18H, OSi (CH 3) 3), 0.58 (m, 2H, CH 2 Cl 2 Si), 2 11.11 (m, 2H, CH 2 CH 2 Si), 5.46 (d, 1H, SiCff = CH), 6.20 (m, 1H, SiCH-CH). 13C NMR (½} (CDCl3): δ = 0.29 ((OTMS) 2SiCH3), 2.07 (OSi (CH3) 3), 16.28 (CH2CH2Si), 29.79 (CH2CH2Si), 125.73 (SiCH = CH), 151.52 (SiCH = CH).

Examples 19A-19F: Cross-linking of polysiloxanes with olefins using (MesPDI) COCH3. A small scintillation vial with 0.002 g (0.004 inmol, 2000 ppm catalyst load) of (MesPDI) COCH3 and olefin was loaded (see Table 7 for specific amounts). The mixture was stirred until a homogeneous pink solution was obtained. Typically, this step required between 5 and 20 minutes of stirring. Polysiloxane (1: 0.75 ratio of C = C to Si-H, Table 7) was then added to the reaction vessel and the mixture was stirred in an oil bath at 65 ° C for 4-6 hours. The resulting gel was ground to a powder using a mortar and pistil, washed with hexanes to remove the byproduct alkane, and vacuum dried overnight. Each sample extracted with hexane was analyzed by nuclear magnetic resonance (NMR) spectroscopy on a Bruker AVANCE 400WB spectrometer operating at a field intensity of 9.40 T; 1H resonance at 400 MHz. Magic-angle rotation (MAS) single pulse excitation (SPE) pulse sequence with a delay of 150 seconds was used for the {1H-13C} or SPE NMR spectra. a 300 second delay for the {1H-29Si} NMR SPE / MAS spectra. Magical angle rotation (MAS) cross polarization (CP) pulse sequence with 10 second delay and a contact time of 5 ms was used for the {1H-13C} NMR CP / MAS spectra. About 0.1 g of each sample was packaged in a 4 mm zirconia rotor (Zr02) rotor with a Kel-F cap and the rotor rotated at ~ 8 to 10.8 kHz for the 29Si and -10.8 kHz data for the data. of 13C. The number of co-added scans was 1000 (13C) or 512 (29Si) for SPE data and 16,000 for CP / MAS 13C data. The process parameters used were 4x zero fill and 5 or 15 Hz LB for 13C or 30Hz for 29Si data.

Table 7. Cross-linking of polysiloxanes with olefins using (MesPDI) CoCH3.

13C NMR Results 1. Olefin: 1-octene The chemical shifts and their designations of the 13C NMR CP / MAS and SPE / MAS spectra of samples from Examples 19A, 19C, and 19E are summarized in Table 8. The spectra show multiple signals observed in three distinct regions of chemical shift, δ 2 to δ -2 consistent with silicon methyl (CH3Si), δ 14 to δ 35 consistent with linear hydrocarbons and δ 124 to δ 135 due to olefin carbons (sp2). No peak is observed at -δ 115 indicating no unreacted residual 1-octene. A comparison of data from two different experiments shows significant differences. There is a significant loss in area for CH2, CH3, and olefin carbons. The results are consistent with the most mobile phase in the sample being saturated and unsaturated hydrocarbons, while the stiffer phase would consist of the structure of the following type, sSiCH2CH2CH2 (CH2) 2CH2CH2CH2Si =. However, in the CP experiment there is still a large amount of olefin signals. This result suggests the presence of unsaturated internal double bond structures (note that the double bond may be in positions 2 to 6), ^ SiCH2CH2CH-CH (CH2) 2ch2ch2ch3.

The two signals observed at δ 125 and δ 131 due to olefin carbons are found at approximately equal intensities. The signals are consistent with the double bond being at position 2 or 6. The CP data for sample 19A shows a very weak peak observed at δ 14 indicating that if the double bond is at position 6 the majority configuration should be trans. The methyl group at position 6 trans, -CH = CHCH3, would overlap the signal observed at δ 18. The weaker signals around δ 130 are consistent with the double bond being at position 3, 4, or 5. .

Table 8. 13C CP / MAS and SPE / MAS NMR intensity data for 1-octene samples (Examples 19A, 19C, 19E) * Areas of all methylene carbons are grouped. 2. Olefin: 1-octadecene The chemical shifts and their designations of the 13 C NMR CP / MAS and SPE / MAS spectra of samples from Examples 19B, 19D, and 19F are summarized in Table 9. The spectra are very similar to those of the samples. 1-octene cross-links where they show multiple signals observed in three distinct regions of chemical shift, δ 2 to δ -2 consistent with silicon methyl (CH3SÍ), δ 14 to δ 35 consistent with linear hydrocarbons and δ 124 to δ 135 due to olefinic carbons (sp2). However, the signal observed at -δ 30 is significantly stronger due to the higher number of methylene groups (CH2) in the 1-octadecene starting material. A second difference in the olefinic chemical shift range is observed. The peak observed at ~ δ 125 is not observed with the same intensity as the peak at ~ δ 131. This result would suggest that the double bond is not near one end, but is internal. The following list summarizes the similarities with the 1-octene data results. • No peak is observed at -δ 115 indicating no residual unreacted 1-octadecene. • SPE and CP data show significant peak area loss for CH2, CH3 and olefin carbons. • The most mobile phase in the sample being saturated and unsaturated hydrocarbons, while the most rigid phase would consist of the structure of the following type, = SiCH2CH2CH2 (CH2) i2CH2CH2CH2Si4. • The CP experiment shows a large amount of olefin signals indicating that the following type structure may be present (note that the double bond may be present at positions 2 to 16), ^ SiCH2CH2CH = CH (CH2) i2CH2CH2CH3. The loss in area of the CH3 peak observed at δ 15 in the CP / MAS experiment may be due to the combination of the methyl group being associated with a mobile phase hydrocarbon molecule and the following structure, sSiCH2CH = CHCH2 (CH2 ) 13CH3, and the intensity of loss is due to the group being at the end of the molecule resulting in greater mobility. The methyl group is further from the cross-linking point. Table 9. 13C NMR CP / ΜΑΞ and SPE / MAS intensity data for 1-octadecene samples (Examples 19B, 19D, and 19F) * Areas of all methylene carbons are grouped.

29Si NMR Results The chemical shifts and their designations of the 29Si SPE / MAS NMR spectra for their Example 19 samples are summarized in Table 10. The observed signal at δ -2 6 is denoted by a D * with the organofunctional group having the double bond at the 2 or allyl position, SiCH2 CH = CHCH2 (CH2) XCH3. This signal is very strong in Example 17A compared to spectra from other samples. Also, there seems to be a slight tendency at this peak being slightly larger when samples are prepared with 1-cetene than with 1-octadecene. The integral of this signal is grouped with the strongest signals observed at δ -22 because of the peak overlap for most samples.

The spectra of the two samples (Examples 19A and 19B) prepared with SiH fluid MD30DHi5M show a large amount of what may be a combination of cyclic D3 and Di species and do not contain a signal at δ -35. Table 10. 29Si SPE / MAS NMR Intensity Data for Examples 19A-19F

In terms of the rheological characteristics of the products, different modules resulting from molecules dependent on cross-linking densities and chain lengths of the binder molecule would be predicted.

Examples 20A-20B: These examples illustrate deuterium labeling experiments that were performed to establish that the occurrence of dehydrogenation hydrosilylation when the reaction of hydrosiloxanes and olefins is catalyzed by (MesPDI) CoCH3.

Example 20A: 1-Octene silylation with (OTMS) 2CH3 Si-D (MDHM-da).

This reaction was performed similar to that of 1-octene silylation with MDHM using 0.050 g (0.45 mmol) of 1-octene, 0.050 g (0.22 mmol, 0.5 equiv.) Of MDHM-dj ( 70% deuterated), and 0.002 g (0.004 mmol, 1 mol%) of (MesPDI) CoCH3. The reaction was rapidly cooled after stirring for one hour at room temperature. Analysis of the 2H NMR spectrum of the product mixture showed incorporation of deuterium into both methyl and octane methylene groups as well as traces of Cb, Cc, and Cd deuterium from 1-bis (trimethyl siloxy) methyl silyl-2 - I understand.

Example 20B: Deuteration of 1-bis (trimethyl siloxy) methyl silyl-2-octene.

In a dry box filled with nitrogen, a J. Young tube was loaded with 0.080 g (0.24 mmol) of 1-bis (trimethyl siloxy) methyl silyl-2-octene, 0.005 g (0.011 mmol, 4 mol%). (MesPDI) CoCH3, and approximately 0.7 mL of benzene-d6. The tube was degassed and received approximately 1 atm of D2. The solution was thawed at room temperature and then placed in an oil bath at 45 ° C for 16 hours. Analysis of the 1 H and 2 H NMR spectra of the product mixture showed partial deuteration of the starting material to the product completely saturated with deuterium mixed along all octyl chains of both compounds. Deuteration occurred mainly at positions C2 and C3, indicating that the unsaturation in the starting material was mainly allyl and not vinyl.

Examples 21A-21D: Olefin Isomerization Experiments. Example 21A shows that (MesPDI) CoCH3 does not isomerize 1-octene.

A small scintillation vial was charged with 0.100 g (0.891 mmol) of 1-octene and 0.004 g (0.008 mmol, 1 mol%) of (MesPDI) CoCH3. The solution was stirred for one hour at room temperature and then quenched by exposure to air. The 1 H NMR spectrum of the product showed only 1-octene and traces of free ligand and no evidence of olefin isomerization. Example 21B shows that 1-octene isomerization with (MesPDI) COCH3 and trisiloxane hydride traces, MDHM was not observed.

This experiment was performed in the same manner as the experiment described above (Example 21A) using 0.100 g (0.891 mmol) of 1-octene, 0.004 g (0.008 mmol, 1 mol%) of (MesPDI) COCH3, and 0.014 g ( 0.063 mmol, 7 mol%) of MDhM. The δ NMR spectrum of the product showed only 1-octene, traces of free ligand and 1-bis (trimethyl siloxy) methyl silyl-2-octene, and no evidence of olefin isomerization. Example 21C illustrates isomerization of α, β-dimethyl allylamine, (CH 3) 2 NCH 2 CH = CH 2 using (MesPDI) COCH 3.

A J. Young tube was charged with 0.017 g (0.20 mmol) of β, Ν-dimethyl allylamine, 0.002 g (0.004 mmol, 2 mol%) of (MesPDI) C0CH3 and approximately 0.7 mL of benzene. -dg. The solution was brought to room temperature and monitored using 1 H NMR spectroscopy. Isomerization of the starting material in N, N-dimethyl-1-propenylamine, (CH3) 2NCH = CHCH3 was 20% complete after 8 hours and 65% after 46 hours. Example 21D illustrates the isomerization of α, β-dimethyl allylamine, (CH 3) 2 NCH 2 CH = CH 2, using (MesPDI) COCH 3 and trisiloxane hydride traces, MDHM.

This reaction was performed in a similar manner to the experiment described above (Example 21C) using 0.091 g (1.1 mmol) of Δ, Ν-dimethyl allylamine, 0.003 g (0.006 mmol, 0.6 mol%) of (MesPDI ) COCH3 and 0.006 g (0.03 mmol, 3 mol%) of MDHM. Isomerization of the starting material in N, N-dimethyl-1-propenylamino, (CH 3) 2 NCH = CHCH 3 was 90% complete after 8 hours and> 95% after 24 hours.

Examples 22A-22C: Propylene silylation with different silanes using (MesPDI) COCH3.

This reaction was performed similarly to that of 1-butene silylation using 0.11 mmol silane (0.025 g MDhM, 0.018 g (EtO) 3SiH or 0.015 g (OEt) 2CH3SiH), 0.001 g (0, 002 mmol) of (MesPDI) COCH 3 and 5.6 mmol (50 equiv) of propylene. Nonvolatiles were analyzed by NMR spectroscopy.

Table 11. Distribution of products for propylene silylation.

Product characterization of Example 20A: 3-bis (trimethyl siloxy) methyl silyl-1-propene. 1H NMR (CDCl3): δ = 0.03 (s, 3H, (OTMS) 2 S (CH3)), 0.09 (s, 18H, OSi (CH3) 3), 1.49 (d, J = 8, 1 Hz, 2H, SiCH 2 CH = CH), 4.86 (d, J = 6.3 Hz, 1H, CH 2 CH = C (H) δ), 4.88 (d, J = 15 Hz, 1H, CH 2 CH = C (Δ) H), 5.77 (m, 1H, CH 2 Cl 7 = CH 2). 13 C NMR (½} (CDCl3): δ = -0.77 ((OTMS) 2S1CH3), 1.97 (OSi (CH3) 3), 25.82 (SiCH2CH-CH), 113.72 (CH2CH = CH2 ), 134.28 (CH 2 CH-CH 2) .1-bis (trimethyl siloxy) methyl silyl propane 1H NMR (CDCl3): δ = 0.00 (s, 3H, (OTMS) 2 SiCH3), 0.09 (s 0.18 (m, 2H, SiCl2 CH2 CH3), 0.95 (t, 3H, SiCH2 CH2 CH3), 1.36 (m, 2H, SiCH2 Cl2 CH3). CDCl3): δ = -0.07 ((OTMS) 2SiCH3), 1.97 (OSi (CH3) 3), 16.75 (SiCH2CH2CH3), 18.05 (SiCH2CH2CH3), 20.37 (SiCH2CH2CH3). Example 22B: 3-Triethoxy silyl-1-propene 1H NMR (CDCl3): δ = 1.22 (t, 9H, OCH2 CH3), 1.67 (d, 2H, SiCff2 CH = CH), 3.84 (q, 6H, OC 17 CH 3), 4.90-5.05 (d, 2H, CH 2 CH = C 12), 5.81 (m, 1H, CH 2 CH = CH 2) 13 C NMR (δ} (CDCl 3): δ = 18.36 (OCH 2 CH 3), 19.34 (SiCH 2 CH = CH), 58.73 (OCH 2 CH 3), 114.85 (CH 2 CH = CH 2), 132.80 (CH 2 CH = CH 2) -1-triethoxy silyl propane 1H NMR (CDCl3): δ = 0.63 (m, 2H, SiCl2 CH2 CH3), 0.97 (t, 3H, SiCH2 CH2 CH3), 1.22 (t, 9H, OCH2 CH3), 1.45 (m, 2H, SYCH2 C 13 C NMR (δ} (CDCl 3): δ = 10.94 (SiCH 2 CH 2 CH 3), 12.92 (SiCH 2 CH 2 CH 3), 16.50 (SiCH 2 CH 2 CH 3), 18.43 (OCH 2 CH 3), 58.40 (OCH 2 CH 3).

Product Characterization of Example 22C: 3-Diethoxy methyl silyl-1-propene. 1H NMR (CDCl3): δ = 0.11 (s, 3H, SiCH3), 1.19 (t, 6H, OCH2 Cl3), 1.63 (d, 2H, SiCH2 CH = CH), 3.76 (q, 4H, OCff 2 CH 3), 4.88 (d, 1H, CH 2 CH = C (Η) H), 4.93 (d, 1H, CH 2 CH = C (Η) H), 5.80 (m, 1H, CH 2 Cl = CH 2 ). 13 C NMR (½} (CDCl 3): δ = -5.19 (SiCH 3), 18.44 (OCH 2 CH 3), 21.92 (Si CH 2 CH = CH), 58.41 (OCH 2 CH 3), 114.45 (CH 2 CH = CH 2), 133.36 (CH 2 CH = CH 2) 1-diethoxy methyl silyl propane 2 H NMR (CDCl 3): δ = 0.08 (s, 3H, SiCH 3), 0.59 (m, 2H, SiCH 2 CH 2 CH 3), 0.94 (t, 3H, SiCH2 CH2 CH3), 1.19 (t, 9H, OCH2 CH3), 1.38 (m, 2H, SiCH2 CH2 CH3) 13 C NMR (XH) (CDCl3): δ = -4.76 ( SiCH3), 16.37 (SiCH2CH2CH3), 16.53 (SiCH2CH2CH3), 18.07 (SiCH2CH2CH3), 18.50 (OCH2CH3), 58.13 (OCH2CH3).

Example 23: Synthesis of (MesPDI) Co-allyl.

A 50 mL round bottom flask was charged with 0.100 g (0.203 mmol) of (MesPDI) CoCl and approximately 20 mL of toluene. The pink solution was cooled in a cold well cooled with liquid nitrogen. Then 0.240 mL (0.240 mmol, 1.2 equiv) of a 1M solution of allyl magnesium bromide in diethyl ether was added dropwise, and the reaction was stirred at room temperature for 3 hours. The solution was filtered through Celite, concentrated to approximately 1 mL and diluted with 3 mL pentane. Recrystallization of the crude product at -35 ° C overnight afforded 0.083 g (0.17 mmol, 82%) of a dark pink powder identified as (MesPDI) Co-allyl (Formula IV): (Formula IV ) Δ NMR (C6D6): δ = 1.61 (s, 6H, N = CCH3), 1.79 (s, 12H, 0-CH3), 2.09 (s, 6H, p-CH3), 5 , 23 (quintet, 1H, 10.4 Hz, allyl-CH), 6.71 (s, 4H, jn-Ar), 7.42 (t, 7.5 Hz, 1H, p-py), 7, 87 (d, 7.5 Hz, 2H, m-py). {1H} 13C NMR (C6D6): δ = 16.72 (N = CCH3), 18.58 (o-CH3), 21.04 (p-CH3), 106.29 (allyl-CH), 115, 42 (p-py), 120.48 (m-py), 129.20 (m-Ar), 130.36 (o-Ar), 134.17 (p-Ar), 147.31 (i-Ar) ), 149.94 (oopy), 167.85 (N = C); not found: allyl CH2 - Catalytic activity evaluation of (MesPDI) Co-allyl. This experiment was performed in a small scintillation vial using 0.100 g (0.891 mmol) of 1-octene, 0.100 g (0.449 mmol, 0.5 equiv) of MDHM and 0.002 g (0.004 mmol, 1 mol%) of (MesPDI). ) Co-allyl. The reaction was monitored by GC and NMR spectroscopy and cooled rapidly before analysis via air exposure. 95% conversion was achieved within 24 hours.

Example 24: Synthesis of (MesPDI) Co-benzyl.

This experiment was performed similarly to the synthesis of (MesPDI) Co-allyl using 0.100 g (0.203 mmol) of (MesPDI) CoCl and 0.026 g (0.20 mmol, 1 equiv.) Of benzyl potassium. The reaction was stirred at room temperature for 16 hours. Recrystallization of the crude product from toluene / pentane 1: 5 at -35 ° C yielded 0.081 g (0.15 mmol, 73%) of a navy blue powder identified as (MesPDI) Co-benzyl (Formula V): (Formula V Analysis for C34 H38 CON3 Calc'd C, 74.57; H 6.99; N, 7.67. Found: C, 74.89; H, 7.14; N, 7.72. 1H-NMR (C6D6): δ = -1.43 (s, 6H, N = CCH3), 1.95 (s, 12H, o-CH3), 2.35 (s, 6H, p-CH3), 2 90 (s, 2H, CoCH 2 Ph), 5.89 (d, 7.5 Hz, 2H, o-benzyl), 6.57 (pseudo t, 7.5 Hz, 2H, m-benzyl), 6.88 (t, 7.5 Hz, 1H, p-benzyl), 7.03 (s, 4H, m-Ar), 7.74 (d, 7.6 Hz, 2H, ni-py), 10.41 ( t, 7.6 Hz, 1H, p-py). 1 H NMR 13 C (C 6 D 6): δ = 3.60 (CoCH 2 Ph), 19.11 (0-CH 3), 21.42 (p-CH 3), 24.81 (N = CCH 3), 117.14 ( p-py), 119.70 (p-benzyl), 123.40 (m-py), 127.20 (o-benzyl), 127.27 (m-benzyl), 129.95 (ffl-Ar), 130.07 (o-Ar), 134.81 (p-Ar), 154.12 (i-benzyl), 154.90 (i-Ar), 157.30 (o-py), 166.46 (N = C).

Catalytic activity evaluation of (MesPDI) Co-benzyl. This experiment was performed in a small scintillation vial using 0.100 g (0.891 mmol) of 1-octene, 0.100 g (0.449 mmol, 0.5 equiv) of MDHM and 0.002 g (0.004 mmol, 1 mol%) of (MesPDI). ) Co-benzyl. The reaction was monitored by GC and NMR spectroscopy and cooled rapidly before analysis via air exposure. 43% conversion was reached after 15 minutes and> 98% after 1 hour.

While the above description contains many specific qualities or conditions, these specific qualities or conditions should not be construed as limitations on the scope of the invention, but merely as examples of preferred embodiments thereof. Those skilled in the art will imagine many other possible variations that will be within the limits of the scope and spirit of the invention defined by the claims appended hereto.

Claims (66)

A process for producing a dehydrogenation silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silyl hydride functional group and (c) a catalyst, optionally in the presence of a solvent, to produce the dehydrogenated silylated product, the catalyst being a complex of Formula (I) or adduct thereof; (Formula I) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl, substituted aryl, or an inert substituent, wherein R1- R5, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and L is hydrogen, allyl, benzyl, SiR3, hydroxyl or a C 1 -C 6 alkyl, substituted C 1 -C 8 alkyl, aryl or substituted aryl group, where R is an alkyl, aryl, or siloxanyl group and L optionally contains at least one heteroatom. A process according to claim 1 further comprising removing the complex and / or derivatives thereof from the silylated product by dehydrogenation. Process according to Claim 1, characterized in that the dehydrogenated silylated product comprises a silane or siloxane containing a silyl group and an unsaturated group. Process according to Claim 3, characterized in that the unsaturated group is in the alpha or beta position relative to the silyl group. Process according to Claim 1, characterized in that the molar ratio of the unsaturated group in said component (a) to the silyl hydride functional group in said component (b) is less than or equal to 1: 1. Process according to Claim 5, characterized in that the silane or siloxane of the dehydrogenation silylated product contains a silyl group derived from component (b). Process according to Claim 5, characterized in that the dehydrogenated silylated product contains two or more silyl terminal groups derived from component (b). Process according to Claim 5, characterized in that it produces an α, ω-substituted alkane or an alkene diol of an alkene or alkane substituted with the Î ±, co-bis (silyl) origin. Process according to claim 1, characterized in that the molar ratio of the unsaturated group in said component (a) to the silyl hydride functional group in said component (b) is greater than 1: 1. Process according to Claim 9, characterized in that the silane or siloxane contains two or more silyl groups derived from component (b). Process according to Claim 1, characterized in that said component (a) is a monounsaturated compound. Process according to Claim 1, characterized in that said component (a) is selected from the group consisting of an olefin, a cycloalkene, an alkyl capped allyl polyether, a functional alkyl capped allyl or metalether polyether. vinyl, an alkyl-capped unsaturated amine, a terminally unsaturated alkyne, acrylate or methacrylate, a vinyl-functional unsaturated aryl ether, polymer or oligomer, a vinyl-functional silane, a vinyl-functional silicone, unsaturated fatty acids, unsaturated esters, and combinations thereof. Process according to Claim 12, characterized in that said component (a) is selected from the group consisting of N, N-dimethyl allylamine, allyloxy substituted polyethers, cyclohexene, linear alpha olefins, olefins. branched olefins, unsaturated polyolefins, a vinyl siloxane of Formula (VIII), and combinations thereof, wherein Formula (VIII) is (VIII) wherein each occurrence of R8 is independently C1-C18 alkyl, C1-6 alkyl Substituted, vinyl, aryl or substituted aryl, and n is greater than or equal to zero. Process according to claim 1, characterized in that said component (b) is selected from the group consisting of RaSiH4_a <(RO) aSiH4-a, HSiRa (OR) 3-a, R3S1 (CH2) f ( SyR20) kSiR2H, (RO) 3Si (CH2) f (SiR20) kSiR2H, QuTvTpHDwDHxMHyMz, and combinations thereof, where Q is Si04 / 2, T is R 'Si03 / 2, TH is HSÍO3 / 2, D is R '2SiO2 / 2, Dh is R'HSiO2 / 2, MH is HR'2SiO1 / 2, M is R3SiO1 / 2, each occurrence of R and R' is independently C1 -C6 alkyl, substituted C1 -C8 alkyl , aryl, or substituted aryl, where R and R 'optionally contain at least one heteroatom, each occurrence of a independently having a value from 1 to 3, f having a value from 1 to 8, k having a value from 1 to 11 , g has a value from 1 to 3, p is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 1000, x is from 0 to 1000, y is from 0 to 20, and z is from 0 to 20, as long as p + x + y is equal ala 3000, the valencies of all elements in the silyl hydride are met. Process according to claim 14, characterized in that p, u, v, y, and z are from 0 to 10, w and x are from 0 to 100, p + x + y = 1 to 100. Process according to claim 1, characterized in that said component (b) has one of the following structures: R1a (R20) t> SiH (Formula IX) (Formula X), (Formula XI), or ( Wherein each occurrence of R 1, R 2, R 3, R 4, and R 5 is independently C 1 -C 18 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, R 6 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkyl. Substituted C1 -C10, aryl or substituted aryl, x and w are independently greater than or equal to 0 (x is at least equal to 1 in Formula X), and b and are integers from 0 to 3 with a + b = 3. Process according to Claim 1, characterized in that the catalyst is a MeB (C6F5) 3 - or, [B [3,5 - (CF3) 2CeH3] 4] ~ salt of the complex of Formula (I). ) · Process according to claim 1, characterized in that at least one of R 6 and R 7 is wherein each occurrence of R 8, R 9, R 10, R 11, and R 12 is independently hydrogen, C 1 -C 18 alkyl, Substituted C1 -C5 aryl, substituted aryl, or an inert substituent, wherein R8-R12, other than hydrogen, optionally contains at least one heteroatom. Process according to Claim 18, characterized in that R 8 and R 12 are independently methyl, ethyl or isopropyl groups and R 10 is hydrogen or methyl. Process according to Claim 19, characterized in that each of R 8, R 10 and R 12 is methyl. Process according to Claim 1, characterized in that R 1 and R 5 are independently methyl or phenyl groups. Process according to claim 1, characterized in that R2, R3 and R4 are hydrogen. Process according to Claim 1, characterized in that the complex is immobilized on a support. Process according to claim 23, characterized in that the support is selected from the group consisting of carbon, silica, alumina, MgCl2, zirconia, polyethylene, polypropylene, polystyrene, poly (amino styrene), polystyrene, dendrimers, and combinations thereof. Process according to claim 23, characterized in that at least one of R 1 to R 7 contains a functional group that covalently binds to the support. Process according to claim 1, characterized in that the catalyst is generated on site by contacting a catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of: a solvent, the silyl hydride, the compound containing at least one unsaturated group, and combinations thereof, the catalyst precursor being represented by Structural Formula (IV) (Formula IV) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C6 alkyl, substituted C1 -C8 alkyl, substituted aryl or aryl, or an inert substituent, wherein R1-R5, other than hydrogen, optionally contains at least one heteroatom; each occurrence of R6 and R7 is independently C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl or substituted aryl, wherein R6 and R7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and X is an anion selected from the group consisting of F ”, Cl-, Br”, I ”, CF3R40SO3- or R50COO-, where R40 is a covalent bond or a C1 -C6 alkylene group, and R50 is a hydrocarbyl group and wherein the activator is a reducing agent or alkylating agent selected from the group consisting of NaHBEt 3, CH 3 Li, DIBAL-H, LiHMDS, and combinations thereof. Process according to Claim 1, characterized in that the reaction is carried out in an inert atmosphere. Process according to Claim 1, characterized in that the reaction is carried out in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof. Process according to Claim 1, characterized in that the reaction is carried out at a temperature of from -40 ° C to 200 ° C. 30. Composition, characterized in that it is produced by a process as defined by any of embodiments 1 to 29, and contains the catalyst and / or derivatives thereof. Composition according to Claim 30, characterized in that it comprises at least one component selected from the group consisting of silanes, silicone fluids and cross-linked silicones. 32. A compound of Formula (II) (Formula II) wherein each occurrence of R 1, R 2, R 3, R 4, and R 5 is independently hydrogen, C 1 -C 6 alkyl, substituted C 1 -C 8 alkyl, substituted aryl or aryl, or an inert substituent, wherein R1-R5, other than hydrogen, optionally contains at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, where R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure. A process for producing a dehydrogenation silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silyl hydride functional group and (c) a catalyst, optionally in the presence of a solvent, to produce the dehydrogenated silylated product, the catalyst being a complex of Formula (III) or adduct thereof; (Formula III) wherein each occurrence of R 1, R 2, R 3, R 4, and R 5 is independently hydrogen, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl, substituted aryl, or an inert substituent, wherein R 4 R5, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R6 and R7 is independently C1 -C18 alkyl, substituted C1 -C18 alkyl, aryl or substituted aryl, wherein R6 and R7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and L is an anionic binder selected from the group consisting of hydrogen, allyl, benzyl, SiR3, hydroxyl, or a C1 -C6 alkyl, substituted C1 -Cig alkyl, aryl or substituted aryl, where R is an alkyl group, aryl, or siloxanyl and L optionally contains at least one heteroatom; Y is a neutral binder; and Q is a non-coordinating anion. A process according to claim 33, further comprising removing the complex and / or derivatives thereof from the silylated product by dehydrogenation. Process according to Claim 33, characterized in that the dehydrogenated silylated product comprises a silane or siloxane containing a silyl group and an unsaturated group. Process according to Claim 35, characterized in that the unsaturated group is in the alpha or beta position with respect to the silyl group. Process according to claim 33, characterized in that the molar ratio of the unsaturated group in said component (a) to the silyl hydride functional group in said component (b) is less than 1: 1. Process according to Claim 37, characterized in that the silane or siloxane of the dehydrogenation silylated product contains a silyl group derived from component (b). Process according to Claim 33, characterized in that the molar ratio of the unsaturated group in said component (a) to the silyl hydride functional group in said component (b) is greater than or equal to 1: 1. Process according to Claim 39, characterized in that the silane or siloxane contains two or more silyl groups derived from component (b). Process according to Claim 33, characterized in that said component (a) is a monounsaturated compound. Process according to Claim 33, characterized in that said component (a) is selected from the group consisting of an olefin, a cycloalkene, an alkyl capped allyl polyether, a functional alkyl capped allyl or metalether polyether. vinyl, an alkyl-capped unsaturated amine, a terminally unsaturated alkyne, acrylate or methacrylate, a vinyl-functional unsaturated aryl ether, polymer or oligomer, a vinyl-functional silane, a vinyl-functional silicone, unsaturated fatty acids, unsaturated esters, and combinations thereof. Process according to Claim 33, characterized in that Q is selected from the group consisting of [B [3,5- (CF3) 2C6H3] 4] ", B (C6F5) 4", Al (OC (CF3 ) 3) <f, CB11H12-, and combinations thereof. Process according to Claim 33, characterized in that Y is selected from the group consisting of dinitrogen (N2), phosphines, CO, nitrosyls, olefins, amines, ethers, and combinations thereof. Process according to Claim 44, characterized in that Y is selected from the group consisting of PH3, PMe3, CO, NO, ethylene, THF, and NH3. Process according to claim 42, characterized in that said component (a) is selected from the group consisting of β, β-dimethyl allylamine, allyloxy substituted polyethers, cyclohexene, linear alpha olefins, olefins branched olefins, unsaturated polyolefins, a vinyl siloxane of Formula (VIII), and combinations thereof, wherein Formula (VIII) is (VIII) wherein each occurrence of R8 is independently C1 -C6 alkyl, C1 alkyl Substituted Cig, vinyl, aryl or substituted aryl, and n is greater than or equal to zero. Process according to claim 33, characterized in that said component (b) is selected from the group consisting of RaSiH4-ai (RO) aSiH4-a, HSiRa (OR) 3-to R3S1 (CH2) f ( SxR20) kSIR2H, (RO) 3Si (CH2) f (SiR20) kSiR2H, QuTvTpHDwDHxMHyMz, and combinations thereof, where Q is Si04 / 2, T is R''Si03 / 2, TH is HSÍO3 / 2, D is R'2S1O2 / 2, Dh is R'HSi02 / 2, MH is HR'2SiOi / 2, M is R3SiO1 / 2 / each occurrence of R and R 'is independently C1 -C10 alkyl, C1 -C16 alkyl substituted aryl, or substituted aryl, where R and R / optionally contain at least one heteroatom, each occurrence of a independently has a value of 1 to 3, f has a value of 1 to 8, k has a value of 1 to 11, g has a value from 1 to 3, p is 0a20, ude0a20, vde0a20, wédeOa 1000, x is 0 to 1000, y is 0 to 20, and z is 0 to 20, as long as p + x + y is equal to wing 3000, the valencies of all elements in the silyl hydride are met. Process according to claim 47, characterized in that p, u, v, y, and z are from 0 to 10, w and x are from 0 to 100, and p + x + y = 1 to 100. Process according to Claim 33, characterized in that said component (b) has one of the following structures: R1a (R20) bSiH (Formula IX) (Formula X), (Formula XI), or (Formula XII ) wherein each occurrence of R1, R2, R3, R4, and R5 is independently C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl or substituted aryl, R6 is hydrogen, C1 -C8 alkyl, C1-6 alkyl Substituted cis, aryl or substituted aryl, x and w are independently greater than or equal to 0 (x is at least equal to 1 in Formula X), and b and are integers from 0 to 3 with a + b = 3. Process according to Claim 33, characterized in that the catalyst is a MeB (C6F5) 3 ~ or, [B [3,5 ~ (CF3) 2C6H3] 4] ~ salt or tetrakis borate salt. (perfluoro aryl) of Formula (III). Process according to claim 33, characterized in that at least one of R 6 and R 7 is wherein each occurrence of R 8, R 9, R 10, R 11, and R 12 is independently hydrogen, C 1 -C 18 alkyl, C 1-8 alkyl. Substituted C1 -C10 aryl, substituted aryl, or an inert substituent, wherein R8-R12, other than hydrogen, optionally contains at least one heteroatom. Process according to Claim 51, characterized in that R 8 and R 12 are independently methyl, ethyl or isopropyl groups and R 10 is hydrogen or methyl. Process according to Claim 52, characterized in that each of R 8, R 10 and R 12 is methyl. Process according to Claim 33, characterized in that R 1 and R 5 are independently methyl or phenyl groups. Process according to Claim 33, characterized in that R2, R3 and R4 are hydrogen. Process according to Claim 33, characterized in that the complex is immobilized on a support. Process according to Claim 56, characterized in that the support is selected from the group consisting of carbon, silica, alumina, MgCl2, zirconia, polyethylene, polypropylene, polystyrene, poly (amino styrene), polystyrene, dendrimers, and combinations thereof. Process according to claim 56, characterized in that at least one of R 1 to R 7 contains a functional group that covalently bonds with the support. A process according to claim 33, wherein the catalyst is generated at the site by contacting a catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of: a solvent, the silyl hydride, the compound containing at least one unsaturated group, and combinations thereof, the catalyst precursor being represented by Structural Formula (IV) (Formula IV) wherein each occurrence of R1, R2, R3, R4, and R5 is independently hydrogen, C1 -C8 alkyl, substituted C1 -C18 alkyl, substituted aryl or aryl, or an inert substituent, wherein R1-R5, other than hydrogen, optionally contains at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 18 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, where R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and X is an anion selected from the group consisting of F ”, Cl”, Br ”, I”, CF3R40SO3 ”or R50COO”, where R40 is a covalent bond or a C1 -C6 alkylene group, and R50 is a hydrocarbyl group C1 -C10; and wherein the activator is a reducing agent or alkylating agent selected from the group consisting of NaHBEt 3, CH 3 Li, DIBAL-H, LiHMDS, and combinations thereof. Process according to Claim 33, characterized in that the reaction is carried out in an inert atmosphere. Process according to Claim 33, characterized in that the reaction is carried out in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof. Process according to Claim 33, characterized in that the reaction is carried out at a temperature of from -40 ° C to 200 ° C. 63. A process for producing a cross-linked material comprising reacting a mixture comprising (a) a silyl hydride-containing polymer, (b) a monounsaturated olefin or an unsaturated polyolefin, or combinations thereof and (c) a catalyst, optionally in the presence of a solvent to produce the crosslinked material, the catalyst being a complex of Formula (I) or adduct thereof; (Formula I) wherein each occurrence of R 1, R 2, R 3, R 4, and R 5 is independently hydrogen, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl, substituted aryl, or an inert substituent, wherein R 1- R5, other than hydrogen, optionally contain at least one heteroatom; each occurrence of R 6 and R 7 is independently C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, aryl or substituted aryl, wherein R 6 and R 7 optionally contain at least one heteroatom; optionally any two of R 2, R 2, R 3, R 4, R 5, R 6 and R 7 together may form a ring being a substituted or unsubstituted, saturated or unsaturated cyclic structure; and L is hydrogen, allyl, benzyl, SIR3, hydroxyl or a C1 -C8 alkyl, substituted C1 -C8 alkyl, aryl or substituted aryl group, where R is an alkyl, aryl or siloxanyl group and L optionally contains at least one heteroatom. Process according to Claim 63, characterized in that the reaction is carried out in an inert atmosphere. Process according to Claim 63, characterized in that the reaction is carried out in the presence of a solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, and combinations thereof. Process according to Claim 63, characterized in that the reaction is carried out at a temperature of from -40 ° C to 200 ° C.