JPS5835200B2 - 0 - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of zero-valent nickel complexes.

It is well known that the zero-valent nickel complex, nickel carbonyl, can be prepared in high yields by introducing carbon monoxide onto finely ground nickel in a carefully controlled temperature range.

L., D., Quin, J., Am., Chem., Soc. 7
Although the reaction of CH3PC12 with elemental nickel produces the complex N1(CH3PC12)4 in good yields, as reported in the literature 9.3681 (1957), phosphorus compounds such as PCl3 and C6H3PC12 It was found that it does not react with elemental nickel.

Similarly, 0-Ca H4CP (C2H=, ) 2'
) 2, C2H4CP (C6H5)2 ) 2 and 9
Aryl-substituted phosphorus compounds such as C6H4(P(C61H5)2)2 have been reported to give zero-valent nickel complexes in slightly lower yields when reacted with elemental nickel (Chatt et al. 0, J
.

Chem, Soc, 1378 (1960): 5504 (
1961)).

Due to the increasing interest in zero-valent nickel complexes as catalysts for oligopolymerization and hydrogen cyanide addition reactions, particularly of aromatic phosphorus compounds, improved synthetic methods for these valuable complexes are needed. It has been pursued.

Nickel O with a ligand like PZ3
An improved method of synthesizing valence complexes has been discovered.

2 in PZ3 is R or OR, R is an alkyl or aryl group having up to 18 carbon atoms, and each 2 of the ligands may be the same or different, but at least 1
The two Z's are OR.

The method of the invention is carried out at temperatures ranging from 0°C to 150°C, preferably from 25°C to 150°C.
A catalyst of the general formula (RIO)
Preferably it consists of reacting with finely divided elemental nickel.

where R and R" are alkyl or aryl groups having up to 18 carbon atoms and may be the same or different, X and 2 have values of 1-2, y is O or 1 and X, y and the sum of 2 is 3, where X is a halide of the group consisting of chloride, bromide and iodide.

The reaction can be carried out using excess glue Gantt as a solvent.

When an organic mononitrile or dinitrile is used as a solvent, the reaction rate becomes faster.

Typical nitriles that may be used include acetonitrile, acrylonitrile, 3-pentenenitrile, methylgeltalonitrile and adiponitrile.

Any organic nitrile that is liquid under the reaction conditions can be used.

Co-solvents such as benzene, toluene, xylene, cresol, cyclohexane or dioxane which are compatible with the organic nitrile can also be used.

The reaction takes place at atmospheric pressure or above atmospheric pressure.
It may be carried out batchwise or continuously in an inert atmosphere such as carbon oxide or an inert gas such as helium, neon, argon or krypton.

1 of zero-valent nickel complexes that can be produced by the method of the present invention
One type has the general formula Ni (PZ3)4,
In the formula, Pz3 is as defined above.

Typical Gantts with the general formula Pz3 include P(OC6H5)3, P(0-nee C6H4CH5)3
, p (op C6H4CH3) s, P(0]
concave and pC6H4CHs)s, P(OC2H5
) a, p (OC4H9) s, C6H3P (0-C
6H3)2, (C6H5) 2 POCa H5.

The corresponding zero-valent nickel complex is Ni(P(OCaH5)s)N1CP(〇-
Sato-C6H4CHa )3 )4,N1(P(OpCa
H4C'H3) s]4, N1(P(0-view and p-Co H4CH3) a)4.Ni(P(C6I(5) (0C6H5)2)4
, Ni (P(C6H5)2(OC6H3) , +4,
Ni (P (OC2H5)s ) Ni (P (O
C4H9)3)+, is included.

Another type of zero-valent nickel complexes that can be produced by the method of the invention are those having the general formula N1(PZ3)2A, where PZ3 is as defined above and A is another unsaturated carbon - Monoolefinic organic compounds without carbon and having 2 to 20 carbon atoms.

The R group of some PZ3 ligands is such that the ligand has at least 13
000 cone angle and such that the carbon-carbon double bond of A is conjugated with a strongly electronegative group such as carbonyl or nitrile as in maleic anhydride, fumaronitrile or acrylonitrile. suitable.

The cone angles mentioned above are J, Am, Chem. Soc,,92
, 2956 (1970) C6A.

Determined as described by Tolman.

Olefins such as ethylene, propylene, butylene, and the like, as well as the olefinic compounds noted above may be used.

Phosphorus ligands meeting the requirement of having a cone angle of at least 13,000 include tri-tolyl phosphite, tri-(2,5-xylyl) phosphite, and tri-(2,5-xylyl) phosphite.
2,4-xylyl), tri-phenyl sulfite, diphenyl phenyl phosphonite, di-
Includes o-tolylphenyl phosphonite and phenyl diphenyl phosphonite.

Suitable zero-valent nickel complexes include N1(P(0-I-C6H4CH5)3]2[C2H4
], N1(P(0 once-C6H4CH3)2[C4H2
O3*] (*C4H203-maleic anhydride) Ni
(P(0Once-C6H4CHs)s)2(C
4H2N2**] (**fumaronitrile) and Ni
(P (0-o -C6H4CH3)3]2-[CH2
-CH-CN].

Under hydrocyanation reaction conditions in the presence of the compound to be hydrocyanated, such as 3-pentenenitrile (3PN), these complexes coordinate with 3PNIJ''-0 valent nickel through the nitrile moiety or through the olefinic moiety. Accordingly, N1((0 once -
C6H4CH3)3]3[NCCH2CH= CH-C
H3) and N1 (0 once C6H4CH3]2[CH3
CH-CH-CH2CN] type complexes.

If PZ3 is a phosphorus ligand such as meta- and para mixed tritrilyl phosphite and its cone angle is less than 130°, N1(PZ3)2 can be prepared by the method of the present invention.
Type A or Ni (PZs) 2 Type A and Ni (
Mixtures with PZ3) type 4 can be made.

In this complex as well, the carbon-carbon double bond of A is preferably conjugated with a strongly electronegative radical such as carbonyl or nitrile.

Zero-valent complexes of the type described above, in which each R group of a given PZ3 ligand is different, can also be prepared by the method of the invention.

A gantt exemplifying this type has a cone angle of 1
Phosphite di-0-) lylphenyl, phosphite di-2-tolyl-p-)lyl, phosphite di-
Gutril-m-)ril, phosphite o-)! J ludiphenol, sulfite o -) ') Lucy p -)
') or phosphorous acid 0-) li-rou-ji-m-) ly-like phosphorus paste-gant, and diphenyl phosphite-p-) Included are phosphorus ligands whose cone angles are less than 1300, such as lylu or phenyl luzi-tolyl phosphite.

The preparation of a zero-valent complex of this type is illustrated in Example 63.

The reaction can be carried out with a stoichiometric amount of nickel relative to the phosphorus paste, or a deficit or excess of nickel can be used.

It is generally recognized that the reaction rate is faster when excess nickel is used.

As mentioned above, the nickel is preferably in finely divided form to provide a large surface area for reaction.

Suitable sources of nickel for this purpose include those available from International Nickel Company (INCO) designated as "reagent grade" and under sample numbers 123128 and 255.

Other forms of elemental nickel can be used, such as those made from Raney nickel or hydrogen-reduced nickel compounds.

As will be appreciated by those skilled in the art, it is desirable that the nickel surface be clean, ie free of oxygen or other substances.

It is preferred to carry out the reaction using an organic nitrile as a solvent.

Best results are obtained when the molar ratio of organic nitrile to nickel is at least 0.5.

Significant excesses of organic nitriles can be used, but the main consideration is economics.

Usually the amount is between 0.5 and 200 molar ratio.

The catalytic compound (R2O) It can be prepared in situ by reaction with a metal halide, a halogen element such as chlorine, bromine or iodine, or the corresponding halide source as an initiator such as hydrogen halide or thionyl halide. can.

Suitable metal halides for this purpose include Cr, N
i, Ti, Cu, Co, Fe, Hg, Sn, Li,
Ca, Ba, Sc, Ce, V, Mn, Be, Ru, R
h, Pd, Zn, Cd, AI, Th, Zr and Hf.

Halides are chlorides, bromides or iodides.

Particularly suitable halides include PX3, TiX4, ZnX
2, Hf X4 and HX, where X is chloride, bromide or iodide.

Mixtures of two or more initiators or catalysts can be used to carry out the reaction.

The zero-valent nickel complexes produced by the process of the invention are particularly useful as catalysts, particularly for the hydrocyanation of olefins.

The present invention is fully illustrated in the examples below.

In the examples described below, the reaction is carried out in a 300 ml flask equipped with a magnetic starch, condenser and thermometer in an inert atmosphere such as nitrogen.

The apparatus was first purged with dry nitride, capped with nitride, and the reactants were charged into the flask, and the nitrite atmosphere was maintained throughout the reaction.

The liquid reaction product was removed from the flask under vacuum through a Buchner funnel attached to the bottom of the flask and analyzed for total nickel and zero-valent nickel.

For all nickel samples, phosphorus pyrosulfite (phosphorus
pyrosulfite) and then dissolved in an aqueous solvent, or the sample can be directly dissolved in methanol, and then quantified by atomic absorption spectrometry.

Zero-valent nickel can be quantified by gel permeation chromatography.

The zero-valent nickel complex has a much larger molecular weight and size than any other component in the reaction medium.

This fact forms the basis for the separation of the complex from lower molecular weight components by gel permeation chromatography on cross-linked polystyrene gels.

Quantitative analysis is performed using a predetermined calibration curve for the complex.

For some complexes such as Ni (PZs) 2 A, the complex Ni (
This is carried out after generating PZ3)2 (CO)2.

Examples 1-4 illustrate the preparation of zero-valent nickel complexes of the type N1(PZ3)4, with Example 4 describing the in-situ preparation of the catalyst for the reaction.

The preparation of N1(PZ3)2 humanoid complexes is illustrated in Examples 5-8, and the catalyst for the reaction is prepared in situ.

The preparation of the catalyst is particularly illustrated in Reference Examples 1-3. Ni(PZ
3) The preparation of a complex containing both 4 Oyohi Ni(Pza) 2A forms is shown in Example 9.

Example 1 Tetrakis(sulfurous acid tolyl and dan-tolyl) nickel (c) A Finely ground nickel powder (manufactured by INCO, reagent grade)
3r13-pentenenitrile 40 f, and undistilled meta-tritolyl phosphite produced during the production and containing approximately 1190 ppm (m and 4-CH5C6H40)2PC1, based on the weight of tritolyl phosphite.
Tritolyl phosphite 801 mixed with para and para was weighed out, dried, and charged into a reactor in a stream of fresh air.

A nitrogen purge gas was maintained while the reaction mixture was rapidly heated to 100° C. and held at that temperature for 4 hours with stirring.

Stop heating and cool the reactor to bring the temperature of the reaction mixture to about 5
The temperature was set to 0°C.

The supply of nitrogen purge gas was stopped; the weight of the reaction product removed from the reactor by the Buchner funnel was 119.
It was 29S'.

Ni(P(0-m and P C6H4CH5)3]4
The concentration of was 45.3%, which corresponded to a conversion rate of 72% from nickel powder to zero-valent nickel in solution.

B The above-mentioned reactants excluding 3-pentenenitrile were reacted at 100°C for 4 hours.

The weight of the product after one serving was 76.63 S'.

Ni(P(0-m and 1-C,I(4CH3)3
) The concentration of 4 was 3.9%.

Example 2 Tetrakis(tri-phosphite and p-)lyl)nickel(o) The same reactants were prepared according to the procedure of Example 1 with 0.2P of NiCl and 0.2f of ZnCl2 at 80%
The reaction was carried out at ℃ for 4 hours.

The product separated by p was 119.691.

The concentration of Ni(P(0-m and 7C6H4CH3)3)4 was 47.4%, which corresponded to a conversion of 76% from elemental nickel to soluble zero-valent nickel.

The catalyst produced in this reaction is (m and p-CH3
C6H4-0)2PCI.

Example 3 Tetrakis(tri-m and p-)lyl)nickel(o) phosphite Among the reactants described in Example 1, acetonitrile was used in place of 3-pentenenitrile, and the reaction was carried out in the same manner at 78°C for 4 hours. Ta.

The product separated by p was 113.42P.

N1CP (0-See and DanC6H4CH3) a)
The concentration of 4 was 51.8%, which corresponded to a conversion rate of 78% from elemental nickel to soluble zero-valent nickel.

The catalyst produced in this reaction was (m and above CH3C
6H4-0)2PCI.

Example 4 Tetrakis (triphenyl phosphite) nickel (o) Raney nickel slurry (50% in water %N1)1.5i was charged.

The flask was evacuated (0.2 mm, 40°C, 20 min) to remove water and then redistilled triphenyl phosphite 6
8 ml was added and the reaction mixture was covered with dry silicone and heated to 110°C in about 35 minutes, then heated to 110-120°C.
The temperature was maintained for 2 hours.

100ml of 3-pentenenitrile was added to the mixture and the mixture was reheated to 110-120°C and held in that range for 2 hours.

The reaction mixture was cooled to room temperature and tested.

No evidence of reaction was observed.

About 0.5f of substantially anhydrous zinc chloride? was added to the reaction mixture, which was then heated to 110-125° C. for 3 hours in nitrogen gas and then cooled to room temperature.

The liquid product was decanted to remove the nickel powder, placed in a bottle and covered with chiron.

Ni(P(OCaH5)a)4 within about 20 minutes
white crystals were separated from the liquid.

The catalyst produced in this reaction is (C6H50)2PC
It is I.

Example 5 Maleic anhydride [bis-(〇-tritolyl phosphite)]
Nickel (0) This example is bulky and gunt phosphorous tree o
-) This exemplifies the production of a zero-valent nickel complex from lyle (cone angle 141°) in a state in which an olefinic compound, that is, maleic anhydride, is added, and furthermore, the catalyst necessary for carrying out the reaction is added in situ. This is an example of manufacturing.

Acetonitrile (25rIl) of maleic anhydride 4.9i
l) Solution, phosphorous acid tree cross-tolyl (Dan-TTP)
3Q1rLl, = Tsukeru powder 31 and TiC140
, 13f was heated in nitrogen gas at 65°C for 20 hours.

The reaction flask was cooled to 0° C. for 2 hours and the crude complex was distributed.

The complex was dissolved in 507711 hot toluene and filtered through a moderate frit.

After that, 200 TLl of methanol was added to precipitate the complex, filtered, and the residue was thoroughly washed with toluene. 27.
25' pure complex N1(P(0-1-C6H4CH5
)3]2[c4H203] was obtained.

This corresponded to a yield of 63%.

N1(o) (calculated value): 6.8%; actual value 6.6%; total Ni (calculated value): 6.8%; actual value 6.8%, 0
．． 59f of unconverted nickel was recovered.

Conversion rate of nickel powder to zero-valent nickel complex is 80%
Met.

The catalysts produced in the above reaction are (O CH3C6H4-O)2PC1 and (o-CH3C6H4
0) PCl3.

The effectiveness of using even small amounts of initiator in the in situ preparation of catalysts for the above reactions is illustrated in the following experiment.

In this experiment, nickel powder was placed in a 125-ml flask with 1.0? (prepared by hydrogen reduction of nickel oxide), o-
TTP20TLl, acetonitrile 10TL11 maleic anhydride 1.0? and TiC14 in the amount shown in the table below (
(microliter) was charged.

The mixture was stirred in nitrogen gas at 65°C for 36 hours,
It was then reacted as described above.

The results are shown in Table 9 form below. In yet another experiment, 1.01 nickel powder, 10TLl
of acetonitrile, 20 ml o TTP and 1.
01 maleic anhydride, however 'l'1
No c14 was added. The reaction mixture was stirred at 20°C for 18 hours; analysis showed no detectable amount of total nickel or no
The valence of nickel was not shown.

Example 6 Acrylonitrile [bis(〇-tritrile phosphite)]
Nickel(0) Following the method of Example 5, a reaction mixture of 1.01 nickel powder, 20 TILl 0-TTP, 10-acetonitrile and 0.05 f iodine was stirred at 20°C for various times and the samples were It was removed and analyzed.

The results are as follows: infrared analysis of the solution of the reaction mixture prepared as described above shows an absorption band at 2200 c1rL-1, which is authentic acrylonitrile [bis(
The absorption band coincided with that of the nickel(0) sample.

The catalyst produced in the above reaction is (.

-CH5C6H4-O)2P■.

Example 7 Fumaronitrile [bis(phosphite-tolyl)]
Nickel (o) According to the method of Example 5: 1. OS' nickel powder, 10 TLl acetonitrile, 21 ml standing-TT
P, 3. (l fumaronitrile and 0.0172 T
The reaction mixture of iCl4 was stirred in nitrogen gas for 6 hours.
After heating at 0°C for 1.8 hours, it was purified and analyzed.

Total nickel was 0.72% and zero-valent nickel was 0.54%, which corresponded to a conversion rate of 17% from nickel powder to fumaronitrile [bis(tri-)lyl phosphite]nickel(0). .

The catalyst produced in this reaction is the same as in Example 5.

Example 8 Ethylene [bis(tri-tolyl phosphite)]nickel (o) 0.51 nickel powder in a 101 rLl pressure tube, 3 m
1 of g-TTP, 1.51 rL of acetonitrile, 0.045' of TiBr4 were charged.

The tube was flushed with 1000 atmospheres of ethylene and heated at 65° C. for 16 hours before the contents of the tube were purified and analyzed.

It was found that zero-valent nickel was 0.1%.

The catalyst produced in the above reaction is (o -CH3C6H40)
2PBr and (o -CH3C6H4-0) PBr2.

The preparation of the catalysts necessary for the synthesis of zero-valent nickel complexes from elemental nickel is also illustrated in Reference Examples 1-3.

Reference example 1 Ditritolyl phosphorous acid and TiCl4 F-tane tetrachloride (1,4P-0,007 mo/l,
) was added to 3P (0,008 mol) of phosphorous acid (2-) trik (o-TTP).

Analysis of the mixture within 5 minutes by 31PNMR spectroscopy showed that 2-tolyl phosphorodichloride)
(0-CH3C6H40PC12) and 9-ditolyl phosphorochloridide (o CH3Ca H40)
2 P CI ) were detected, indicating that o-TTP was fully reacted.

Reference example 2 9-tritolyl phosphorous acid and ZrCl4 zirconium tetrachloride (0,12?-0,0005 mol)
P (0,008 mol) was added to o,-TTP.

After heating the mixture to dissolve the ZrCl4, the mixture was held at 94° C. for 30 minutes.

As a result of analyzing the mixture by 31PNR, the area ratio of (o- CH3C6H,0)2 PCI 10-'r T P is the theoretical value of the area ratio when all ZrCl4 reacts.

Compared to that, it showed 1/4.7.

Reference example 3 Phosphite 6-) litryl and HfCl4 hafnium tetrachloride (0,16f!-0,0005 mol)
was added to the TTP at 31 ('o, oos mol) and the mixture was heated to dissolve the HfCl4 and then heated at 94°C for 3.
It was held for 0 minutes.

As a result of analysis by 31PNMR, (o-CH3C6H
40) The area ratio of 2PCI10-TTP is 1/1 compared to the theoretical value of the area ratio when all Hf C14 reacts.
It showed 0.5.

Example 9 Tetrakis (tri-m and p-tolyl phosphite) nickel (0) and maleic anhydride [bis (tri-m and p-tolyl phosphite)] nickel (o) manufactured by INC0 in a 1257d flask. Reagent grade nickel powder 1'? , maleic anhydride 2z, 3-pentenenitrile 20? and approximately 800 ppm (m and CH3Ca H40) based on the weight of tritolyl phosphite.
A mixture of meta- and para-phosphite tritolyl 121 containing 2 PCl was charged and mixed in nitrogen gas at 25°C.

Mixing in nitrogen gas continued for 46 hours, and analysis of the sample taken during that time showed 1.29% by weight of nickel(0), which is due to the conversion from nickel powder to zero-valent nickel in the solution. This corresponded to a conversion rate of 44%.

After further mixing for up to 115 hours, the analysis results showed that 1
．． It showed 81% by weight of nickel(0), which corresponded to a 61% conversion from nickel powder to zero-valent nickel in solution.

In the analysis by 31PNMR, N1(P(0-■ and I
) C6H4CH5)3)4 and Ni(P(0-m
and p-C6H4CH5)3]2[C4H2O3*].

Examples 10-62 The examples summarized in Table 1 further illustrate the in situ preparation of the catalysts necessary for the synthesis of Ovalent nickel complexes from elemental nickel.

The following abbreviations have been used in Table 1: P'rTP, tri-p-)lyl phosphite; 0TTP, tri-o-tolyl phosphite; TTP, mixture of trimeta- and para-tolyl phosphite; 3PN; 3-pentenenitrile; ADN, adiponitrile: MGN, 2-methylgeltaro *C4H203-maleic anhydride nitrile;
cyane, cyclohexane.

In all examples, the amount of finely ground nickel used was 1
It was 2.

However, in Experiment 25, the amount used in a) was 1.52.
It means that it was.

The notation Mb) given in some experiments indicates that the volume unit is 1 microliter (0,001 ml).

Example 63 Ni such that each R group of the Mz3 ligand is different
The preparation of zero-valent complexes of the (M2S) type 4 is illustrated in several experiments in Example 63.

In this example, the ligand was a triaryl phosphite in which the R groups of this ligand were erect-tolyl and phenyl groups.

The required triaryl phosphite is obtained by reacting phosphorus trichloride with a specific mixture of 0-cresol and phenol, previously dried over molecular sieves, and converting the mixture to 100%
℃ overnight and heat the mixture at 200℃ with nitrogen purge gas for an additional 4 to 6 hours or until the chloride value reaches the required or desired value to chlorinate the by-product. Prepared by removing hydrogen.

To produce a zero-valent nickel complex from a mixed triaryl phosphite, the mixed triaryl phosphite (100 r
) to 3i nickel powder (Inc.

Co., Ltd., reagent grade) and 4M' of 3-pentenenitrile, and the mixture was heated at 80°C for 3 hours.
Hold at 5°C for 16-18 hours.

The results obtained using various amounts of triaryl phosphites prepared with O-cresol and phenol are shown in the table below.

The catalyst produced in the above reaction is P-(0-.

C6H4CH5)2C1 and P-(0-C6H,t)2
C1 and P (0-0-C6H4CH3)-0(C6H
5) CI.

To summarize the present invention: (1) Ni (M2S)4 and Ni (M2S)
2 M in A is from the group consisting of P, As and sb, 2 is R or OR, R is an alkyl or aryl group having up to 18 carbon atoms, and at least one 2 is OR; Each R group in 3 may be the same or different (and A is a monoolefin system having 2 to 20 carbon atoms with no other carbon-carbon unsaturated bonds). is an organic compound, in which the elemental nickel has the general formula (RIO)xR''yMX2, where M is As defined above, R1 and R" are alkyl or aryl groups having up to 18 carbon atoms and are the same or different, in which X and 2 have a value of 1 to 2. and y is 0 or 1, the sum of X1y and 2 is 3, and X is a halide from the group consisting of -ci, -Br and -I. Both are present at 5 mol/million mol,
In addition, for the production of Ni(■'3) 2 A, a group of zero-valent compounds consisting of Ni(I)4 and Ni(R)2A are reacted in the presence of a monoolefin organic compound A. A method for producing a nickel complex.

(2) The method of item (1), wherein the reaction is carried out at a temperature in the range of 25 to 100°C and with the addition of an organic nitrile.

(3) The method of item (2) in which M2S is Pz3.

(4) The method of item (3), wherein Pz3 is triaryl phosphite.

(5) The triaryl phosphite is triphenyl phosphite, triphenyl phosphite p-) 1,1l, phosphorous acid)
') -m-)') and phosphite tri(m and p
-) Lil).

(6) The catalytic compound (R2O) The method of item (2), wherein the halogen elements are alkyl-substituted halides, metal halides, halogen elements of the group consisting of C1□, Br2 and I2, and their corresponding hydrogen halides and thionyl halides.

(7) The initiator is PX3, TiX4, ZrX4, HfX,
and 1, in which X is -C1, -Br or 1, and I2.

(8) For a certain Pz3, its cone angle is at least 130
The method of paragraph (3), in which the R group is chosen to be 0 and compound A is present.

(9) The method according to item (8), wherein A is a monoolefinic organic compound having a strong electronegative group conjugated with a carbon-carbon double bond of an olefin.

(10) The method of item (9), wherein the monoolefinic organic compound is from the group consisting of maleic anhydride, acrylonitrile, and fumaronitrile.

(11) PZ3 is phosphorous acid)! J -o-) Lyle, tri-phosphite 〇-phenyl phenyl, tri-phosphite 2,5-xylyl and tri-phosphite 2,4-
The method of paragraph (8), which is of the group consisting of xylyl.

Claims (1)

[Claims] An improved method for preparing a complex of decavalent nickel and an organophosphorus ligand, comprising: elemental nickel with an organophosphorus ligand and an organo-substituted phosphorus halide in an amount of at least 5 moles/million moles relative to the amount of said ligand. A manufacturing method consisting of reacting in the presence of.