BACKGROUND OF THE INVENTION Field of the Invention The invention pertains to a method for the electrochemical production of Ni (0) phosphite or diphosphite complexes in an electrolyzer, using direct or alternating current. The invention also relates to phosphite and diphosphite complexes and their use, for example, as catalysts.

Description of Related Art European Patent Application No. 0 715 890 A1 describes a method for producing a catalyst based on transition metal phosphines; B. Corain, G. Bontempeli, L. de Nardo, Gan-Antonio Mazzocchin, Inorganica Chimica Acta, 26 91978), 37, describe a method for producing a Ni (o-TTP) complex by anode dissolution of metallic nickel in acetonitrile with subsequent electroreduction of the nickel ions on a mercury cathode; M. Mori, Y. Hashimoto, Y. Ban, Tetrahedron Letters, 21 (1980), 63, describe a method for generation of a Ni (PPh3) 4 complex by electrochemical reduction of NiC12 (PPh3) 4, PPh3 in dimethylformamide (DMF) in a diaphragm electrolyzer, using a Pb cathode and a Pt anode.

Coordination compounds of some transition metals are active homogeneous catalysts in reactions of organic compounds, especially in hydrocyanation processes.

Electrochemical methods for production of such catalysts are especially preferred, because the sources of metal ions can be accessible and easily prepared and the electrode can be placed in an adiponitrile (ADN) synthesis reactors (in a second stage). The electrode can be fully inert and activated by supplying the necessary voltage, once there is a need for a catalyst in the process. The concentration of metal ions in solution is proportional to the total amount of charge passed through the

electrolyzer. Consequently, the amount of catalyst can be easily controlled by the amount of energy passed through the electrolyzer.

Electrochemical production of phosphite complexes of Co and Ni have been investigated. The process comprises two stages: anode dissolution of Co or Ni and subsequent cathode reduction of M2+ in the presence of excess corresponding phosphorus ligands. Published articles on electrosynthesis of complexes are mostly devoted to investigating electrochemical behavior, some physical properties and the effect of nature of the tricovalent phosphorus ligands on the relative stability of Ni (III), Ni (I) and Ni (0) complexes. G. Bontempelli, F. Magno, G. Shiavon, B. Corain, Inorg.

Chem., 20 (1981), 2579.

The shortcomings of the published results on direct and indirect electrosynthesis of Ni (0) complexes include electrodeposition of a finely ground metallic nickel on the surface of the cathode, despite the 15-500-fold excess of phosphorus ligand, the low yield of substance and the low current yield. Published results cannot be used as a basis for developing even a laboratory method for preparation of Ni (0) complexes.

Summarv of the Invention There is thus a desire to provide new methods of making Ni (0) complexes and to provide Ni (0) complexes that are improved over those in the art.

In one embodiment, the invention provides a method for the electrochemical production of a phosphite or diphosphite Ni (0) complex comprising: (a) dissolving metallic nickel from an anode in an aprotic solvent in a diaphragmless electrolyzer containing the anode and cathode to produce Ni 2+ nickel ions, and (b) electroreduction o the nickel ions on the cathode in the presence of one or more phosphorus ligands by direct or alternating current, to thereby produce the complex.

In an alternate embodiment, the invention provides a method for the electrochemical production of a phosphite or diphosphite Ni (0) complex comprising:

(a) dissolving metallic nickel from an anode in an aprotic solvent in a diaphragmless electrolyzer containing the anode and cathode to produce Ni 2+ nickel ions, and (b) reducing the nickel ions in solution in the presence of one or more phosphorus ligands by using a metal that is more electropositive than nickel, thereby producing oxidized nickel, and (c) electroreducing and depositing said oxidized nickel at the cathode, thereby producing the complex.

Further objects, features, and advantages of the invention will become apparent from the detailed description that follows.

Detailed Description of Preferred Embodiments The invention pertains to an electrochemical method for producing phosphite and diphosphite Ni (0) complexes in a diaphragmless electrolyzer, containing a cathode and anode, by anode dissolution of metallic nickel in an aprotic solvent with subsequent electroreduction of the nickel ions on the cathode in the presence of phosphorus ligands, using direct or alternating current.

The anode comprises nickel as the source of the produced Ni (0) complex. As discussed below, an additional anode can be used, e. g., to produce a Lewis acid. A preferred second anode is a zinc anode.

In the process of the invention, the anode can be in any form, including wire, rod, plate, or foam. Wire is often preferred because of its higher surface area.

The cathode preferably comprises a metal with low hydrogen overvoltage.

"Low"means the overvoltage is close to the theoretical potential for hydrogen discharge. Useful metals includes platinum, gold, palladium, ruthenium, iridium, cobalt, molybdenum, nickel and iron.

Any desired phosphorus ligands can be used. Suitable phosphorous ligands include bidentate phosphorous-containing ligands such as bidentate phosphites, bidentate phophinites, bidentate phosphonites and bidentate phosphines. Most preferred ligands are bidentate phosphite ligands.

Suitable bidentate phosphite ligands are of the following structural formulae: (R10) 2P (OZO) P (OR1) 2,

In these formulae, Rl is phenyl, unsubstituted or substituted with one or more Ci to Ci2 alkyl or Cl to C12 alkoxy groups; or naphthyl, unsubstituted or substituted with one or more Ci to C12 alkyl or C, to C12 alkoxy groups.

Z and Z'are independently selected from the groups consisting of structural formulae I, II, III, and IV: wherein: R2 and R9 are the same or different, and are selected from H, Cl to Ci2 alkyl, and Ci to C12 alkoxy; R3 and R8 are the same or different, and are selected from H, C, to C12 alkyl, and Cl to C12 alkoxy; R4 and R7 are the same or different, and are selected from H, Cl to C12 alkyl, and Ci to Cl2 alkoxy; R5 and R6 are the same or different, and are selected from H, Cl to C12 alkyl, and Ci to C12 alkoxy;

wherein: X is O, S, CH (R18), or C (Rl8) (R'9); R10 and Rl7 are the same or different, and are selected from H, Ci to C12 alkyl, and Cl to C12 alkoxy; R11 and R16 are the same or different, and are selected from H, Cl to C12 alkyl, and Ci to C12 alkoxy; R12 and R15 are the same or different, and are selected from H, C, to Ci2 alkyl, and Ci to C12 alkoxy; R13 and R14 are the same or different, and are selected from H, Cl to C12 alkyl, and Ci to C12 alkoxy; and Rl8 and Rl9 are independently H or Ci to C12 alkyl; wherein: R20 and R21 are the same or different, and are selected from H, C, to C12 alkyl, and Ci to C12 alkoxy; and CO2R22, R22 is C, to C12 alkyl or C6 to C, 0 aryl, unsubstituted or substituted with C, to C4 alkyl groups. The aryl groups are preferably phenyl or naphthyl.

wherein: A is CH(R24);S, R23 and R24 are the same or different, and are selected from H and C02R25; R25 and R26 are H or Ci to C12 alkyl; R27 is C, to Ci2 alkyl.

In the above structural formulae, the C, to Ci2 alkyl, and Ci to C12 alkoxy groups may be straight chains or branched, substituted or unsubstituted. Any substituent can be used that does not undesirably interfere with the process Examples of ligands that can be used in the present process include those having the formulae V to XXTV, shown below.

V (where iPr is isopropyl) VI (where iPr is isopropyl) (where R34 is methyl or ethyl)

(where R35 is methyl, ethyl, or isopropyl)

XV (where iPr is isopropyl) XVI (where iPr is isopropyl)

Suitable bidentate phosphites are of the type disclosed in U. S. Patents 5,512,695,5,512,696,5,663,369, and 5,723,641, the disclosures of which are incorporated herein by reference. Suitable bidentate phosphinites are of the type disclosed in U. S. Patents 5,523,453 and 5,693,843, the disclosures of which are incorporated herein by reference.

Monodentate phosphites are also suitable ligands for the process of the invention. Examples of suitable monodentante phosphite ligands are shown by structures XXVII and XXVHI: wherein: R'and Z are as previously defined above.

Specific examples of monodentate phosphite ligands suitable for this process include the following representative examples:

The present invention has advantages over prior methods for direct electrosynthesis of phosphite and diphosphite Ni (0) complexes, which can be used as catalysts. These advantages include: i. obtaining higher yield, for example, from 50 to 100% phosphite and diphosphite Ni (0) complexes, depending on the nature of the ligand and the nature of the solvent; ii. the ability to use in the cathode reaction, complex ions of nickel Ni (acac) 2 in acetonitrile and dimethylformamide solutions (these are weakly coordinating solvents) and Ni2+ ions coordinated with 3- pentenenitrile in 3-pentenenitrile solution; iii. the ability to use cathode materials with low hydrogen overvoltage, preferably a nickel electrode; iv. the ability to use in the concluding stage, of electrosynthesis of Ni (0) complexes, i. e., after use of a nickel anode, of a dissolving zinc anode or anodes from group I, II, IV, V, VI, VII and VIII metals. Useful metals are not limited by but include: Na, Li, Mg, Ca, Ba, Sr, Ti, V, Fe, Cr, Mn, Co, Cu, Zn, Cd, Al, Ga, In, Sn, Pb, and Th, with Zn being preferred. This permits elimination of anode oxidation of the end

products and simultaneous introduction of a Lewis acid to the catalytic system, which favorably affects the subsequent chemical conversions with participation of the catalysts. In contrast, in European Patent Application of Rhone-Poulenc No. 0715890, the Lewis acids were introduced to the cathode chamber of the electrolyzer from the outside.

The present process enjoys major advantages in comparison with the prior methods: points (ii) and (iii) prevent electrodeposition of metallic nickel on the electrode surface. Also, the developed method can use phosphorus ligands in amounts that correspond to the equimolar amount of dissolved nickel.

The complexes thus produced are useful as catalysts, for example, for olefin hydrocyanation and alkene nitrile isomerization. Specific examples are the hydrocyanation of butadiene to produce 2-methyl-3-buenenitrile and 3-pentenenitrile, the hydrocyanation of 3-pentenenitrile to adiponitrile, and the isomerization of 2- methyl-3-butenenitrile to 3-pentenenitrile. These complexes are also potentially useful as catalysts and reagents for other chemical transformation, such as coupling reactions.

In Examples I through XXVII that follow, electrosynthesis of phosphite and diphosphite Ni (0) complexes was run in a diaphragmless electrolyzer equipped with a water jacket, reflux condenser, and two nickel electrodes. In Example XXVIB, electrosynthesis of diphosphite Ni (0) complex was run in a diaphragmless electrolyzer equipped with a single nickel anode and a copper cathode. The solvents used should have a suitable dielectric, in which the ligands and optional electrolyte are soluble.

The solvents include (acetonitrile (AN), dimethylformamide (DMF), or 3- pentenenitrile (3-PN)), using Bu4NBr as background electrolyte. A background electrolyte is a salt that adds conductivity, but does not participate in the reaction. Any desired background electrolyte can be used. For example, other organo-ammonium electrolytes may be used provided that they are soluble in the solvent chosen AN, DMF, 3-PN for preparative electrolysis and voltamperometry were purified according to generally adopted methods. 3-PN was purified by distillation under vacuum in an argon atmosphere. The solution during electrosynthesis was continuously agitated on a magnetic stirrer and scavenged with high purity argon. When electrolysis was run in the presence of acetylacetone (acac), the molar ratio of Ni2+: acac was 1: 2, the amount of electricity corresponded to full conversion of the dissolved Ni2+ ions in Ni (acac) 2,

whereupon the ligand was added and an amount of electricity equivalent to the added ligand passed through.

The ingredients, e. g. solvent, liquid, and electrolyte, can be present in any proportion so long as the intended production of the Ni (0) complex is achieved.

A preferred molar ratio of dissolved nickel ions to phosphite ligand was Ni2+: P (OR) 3 = 1: 4 to 1: 20. A preferred ratio of dissolved nickel ions to diphosphite ligand was Ni2+: diphos = 1: 1 to 1: 8 Acceptable ranges are Ni2+: P (OR) 3 = 1: 2 to 1: 40; Ni2+ : diphos = 2: 1 to 1: 20.

The ligands can be monophosphite ligand with a generic structure P (OAr) 3 (see structure XXVH),-diph+osphite ligands of generic structure (ArO) 2POZOP (OAr) 2 (see structure on pg 3), or sterically hindered diphosphite ligands of the same generic structure as a nonsterically hindered ligand, with the exception that the hydrocarbyl substiuents on the various aromatic rings are large enough to prevent two such ligands from simultaneously coordinating to nickel.

The produced complexes can have generic structures: (i) Ni (bidentate diphosphite) 2, (ii) Ni (monodentate phosphite) n, wherein n=3 or 4, or (iii) Ni (bulky bidentate diphosphite) Lm, wherein L= a neutral electron donor ligand such as an olefin, andm= 1 or2.

Preparative electrolysis and recording of voltamperograms were carried out on a PAR model 273 potentiostat/galvanostat. Analysis of the phosphite and diphosphite Ni (0) complexes was accomplished using cyclic voltamperometry on a glass-carbon electrode. The 3'P-NMR spectra were obtained on a Bruker WP-80SY 32.4 MHz spectrometer (internal standard 85% phosphoric acid) and by ultimate analysis.

Phosphite ligands based on p-tritolyl phospite (p-TTP), o-tritolyl phosphite (o- TTP) and trimethyl phosphite (MeO) 3P, as well a diphosphite ligands based on pyrocatechol, 2-2'-bis (phenol) and bis (naphthol) were used as ligands. Unless otherwise indicated, the ligands were prepared by methods known to those skilled in the art, such as described in U. S. Patent Nos. 5,663,369,5,512,696, and 5,512,695, or acquired from Aldrich.

Nickel and zinc anodes and nickel cathodes were preferred in the electrosynthesis processes. Galvanostatic electrolysis is one done by constant current.

The invention is illustrated by the following non-limiting examples.

Example I Galvonostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL AN, 0.6 g (1.86 mmol) Bu4NBr, and 2.0 g (5.7 mmol) p- TTP.

The galvanostatic electrolysis was carried out at a current of 60 mA and 25°C.

108 mAh of electricity was passed through. The 2.0 g (5.7 mmol) of p-TTP ligand was introduced after 26 mAh of electricity had been passed through. After completion of electrolysis, the electrolyte was filtered, and a three-fold volume of methanol was added to the filtrate and it was filtered again after 30 minutes. The Ni (p-TTP) 4 precipitate was washed with methanol and dried in vacuum for 5 hours. 0.3 g Ni (p- TTP) 4 was isolated. Current yield (CY)-15%.

Example Galvonostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL AN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acetylacetone (acac), and 2.0 g (5.7 mmol) p-TTP.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 96 mAh of electricity was passed through. The 2.0 g (5.7 mmol) of p-TTP ligand was introduced after 20 mAh of electricity had been passed through. The complex was isolated as described in Example 1.0.48 g Ni (p-TTP) 4 was isolated. Current yield (CY)-24%.

Example in Galvonostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL DMF, 0.6 g (1.86 mmol) Bu4NBr, and 2.0 g (5.7 mmol) p- TTP The galvanostatic electrolysis was carried out at a current of 60 mA and 25°C.

136 mAh of electricity was passed through. The 2.0 g (5.7 mmol) of p-TTP ligand was introduced after 60 mAh of electricity had been passed through. The complex was isolated as described in Example 1. < 0.1 g Ni (p-TTP) 4 was isolated. Current yield (CY) < 5%.

Example IV Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL DMF, 0.6 g (1.86 mmol) Bu4NBr, 0.3 g (3 mmol) acetylacetone (acac), and 2.0 g (5.7 mmol) p-TTP. ACAC is a ligand for the Ni2+ which is generated electrochemically.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 156 mAh of electricity was passed through. The 2.0 g (5.7 mmol) of p-TTP ligand was introduced after 80 mAh of electricity had been passed through. The complex was isolated as described in Example 1.1.0 g Ni (p-TTP) 4 was isolated. Current yield (CY) equals 50%.

Example V Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 2.0 g (5.7 mmol) p- TTP

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 111 mAh of electricity was passed through. The 2.0 g (5.7 mmol) of p-TTP ligand was introduced after 35 mAh of electricity had been passed through. Ni (p-TTP) 4 was not isolated. Current yield (CY)-37.7%. The current yield was calculated based on the voltamperogram according to the equation of Rendels-Shevchik, see Z. Galyus, Theoretical Fundamentals of Electrochemical Analysis. Translation. Moscow. Mir.

Publishers 1974, page 133.

Example VI Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acetylacetone (acac), and 2.0 g (5.7 mmol) p-TTP.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 104 mAh of electricity was passed through. The 2.0 g (5.7 mmol) of p-TTP ligand was introduced after 28 mAh of electricity had been passed through. Ni (p-TTP) 4 was isolated, as described in Example 1.0.75 g Ni (p-TTP) 4 was isolated. Current yield (CY)-37.0% and 52.8% (determined before isolation, based on the voltamperogram according to the Rendels-Shevchik equation). 15.8% of the complex was lost during isolation.

Example VII Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acetylacetone (acac), and 2.0 g (5.7 mmol) o-TTP.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 117 mAh of electricity was passed through. The 2.0 g (5.7 mmol) of o-TTP ligand was introduced after 40 mAh of electricity had been passed through. Ni (o-TTF) 4 was not

isolated. Current yield (CY) 26.0% (determined on the voltamperogram according to the Rendels-Shevchik equation).

Example Vin Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 1.0 g (8.1 mmol) (MeO) 3P.

Galvanostatic electrolysis was run at a current of 60 mA and 25°C. 120 mAh of electricity was passed through. The 1.0 g (8.1 mmol) (MeO) 3P ligand was introduced after 17 mAh of electricity was passed through. The complex was isolated as described in Example 1.0.3 g Ni [(MeO) 3P] 4 was isolated. The current yield (CY)- 100%. (CY was determined based on the voltamperogram according to the Rendels- Shevchik equation).

Example IX Electrosynthesis of diphosphite Ni (0) complexes based on pyrocatechol derivatives (PD) Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acetylacetone (acac), 0.8 g (2.1 mmol) PD. These reagents were obtained from Aldrich Chemical Company.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 89 mAh of electricity was passed through. The 0.8 g (2.1 mmol) of PD ligand was introduced after 28 mAh of electricity had been passed through. The complex was isolated as described in Example 1.0.45 g Ni (PD) 2 was isolated. Current yield (CY) 100.0%. CY was determined from the voltamperogram according to the Rendels- Shevchik equation.

Example X Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 1.05 g (2.8 mmol) PD.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 100 mAh of electricity was passed through. The 1.05 g (2.8 mmol) of PD ligand was introduced after 20 mAh of electricity had been passed through. The Ni (PD) 2 was not isolated. Current yield (CY) 100.0%. CY was determined from the voltamperogram according to the Rendels-Shevchik equation.

Example XI Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 20 mL AN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acac, and 1.05 g (2.8 mmol) PD.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 91 mAh of electricity was passed through. The 1.05 g (2.8 mmol) of PD ligand was introduced after 20 mAh of electricity had been passed through. The Ni (PD) 2 complex was not isolated. Current yield (CY) 100.0%. CY was determined from the voltamperogram according to the Rendels-Shevchik equation.

Example XII Electrosynthesis of diphospite nickel (0) complexes based on 2,2'-biphenol derivatives Ligand A

Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 40 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 1.3 g (2.12 mmol) ligand A. Ligand A was prepared analogous to the literature method (P. Pringle, et al., J. Chem. Soc., Chem. Commun. (1991), (12), 803-4).

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 102 mAh of electricity was passed through. The 1.3 g (2.12 mmol) of ligand A was introduced after 20 mAh of electricity had been passed through. The complex Ni (A) 2 was not isolated. Current yield (CY) was 36.3%. CY was determined from the voltamperogram according to the Rendels-Shevchik equation.

Example XIH Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 30 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acac, and 1.3 g (2.12 mmol) ligand A.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 99 mAh of electricity was passed through. The 1.3 g (2.12 mmol) ligand A was introduced after 20 mAh of electricity had been passed through. The complex Ni (A) 2

was isolated as described in Example 1.0.3 g Ni (A) 2 was isolated. Current yield (CY) 44.4.0%. According to 31P-NMR, the isolated product contained 75% diphosphite Ni (0) complex and 25% of the initial ligand A.

Example XIV Ligand B Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 20 mL AN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acac, and 1.3 g (2.88 mmol) ligand B. Ligand B was prepared analogous to the method described in Batalova, T. A., et al., Russ. J. Gen. Chem. (1998), 68 (10), 1570-1579.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 112 mAh of electricity was passed through. The 1.3 g (2.88 mmol) of ligand B was introduced after 22 mAh of electricity had been passed through. The Ni (B) 2 was isolated as described in Example 1.0.77 g Ni (B) 2 was isolated. Current yield (CY) 59.0%.

Diphosphite ligands: Ligand 115A Ligand 115B Ligand 115C (ArO) 2PP (OAr) 2 (afro) 2pso O, P (OAr) 2 (ArOzPP (OAr) 2 < : < < OAr = oç OAr = °9 OAr = °9Et Et Molecular weight: Molecular weight: Molecular weight: 730.78 814. 94 786.89 The sterically hindered diphosphite ligands are prepared by methods known to those skilled in the art. For instance, the preparation of ligand 115A is described in WO 9906358. Ligands 115B and 115C were prepared similarly from C1P (0-2- EtC6H4) 2 and 3,3', 4,4', 6,6-bis-2,2'-phenol or 3,3', respectively.

In the case of sterically hindered bis (phosphite) ligands 115A, 115B and 115C, the complexes (115A) 2Ni, (115B) 2Ni, or (115C) 2Ni could not be prepared. In examples XV, XVI and XVII, the possibility of formation of 115ANi (3-PN) x, 115BNi (3-PN) X and 115CNi (3-PN) x complexes was demonstrated.

Example XV Ligand 115A Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a

nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 25 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 1.84 g (1.15 mmol) 115A.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 92 mAh of electricity was passed through. The 1.84 g (1.15 mmol) of ligand 115A was introduced after 30 mAh of electricity had been passed through. Complex 115ANi (3- PN) x was not isolated. Substance yield (SY) and current yield (CY) were 66.0% (determined according to the voltamperogram).

Example XVI Ligand 115B Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 25 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.74 g (0.9 mmol) 115B.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 77 mAh of electricity was passed through. The 0.74 g (0.9 mmol) of ligand 115B was introduced after 28 mAh of electricity had been passed through. Complex 115BNi (3- PN) X was not isolated. Substance yield (SY) and current yield (CY) were 46.8% (determined according to the voltamperogram). Example XVII Ligand 115C

Galvanostatic electrolysis was run in-a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 4 cm2). The following were charged to the electrolyzer: 25 mL E-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.72 g (0.92 mmol) 115C.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 78 mAh of electricity was passed through. The 0.72 g (0.92 mmol) ligand 115C was introduced after 28 mAh of electricity had been passed through. Complex 115CNi (3- PN) x was not isolated. Substance yield (SY) and current yield (CY) were 77.9% (determined according to the voltamperogram).

Electrosynthesis of LNi (crotyl) CNZnBr2 complexes based on 2,2'-biphenol derivatives, 115A, 115B and 115C ligands.

Example XVIII Ligand 115A Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 25 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 1.0 g (1.37 mmol) 115A.

Galvanostatic electrolysis was run at a current of 60 mA and 25°C. 144 mAh of electricity was passed through. The 1.0 g (1.15 mmol) ligand 115A was introduced

after 30 mAh of electricity had been passed through. After 104 mAh of electricity had been passed through, the Ni anode was replaced with Zn and electrolysis continued.

After dissolution of the Zn anode (surface area 4 cm2) (amount of electricity 40 mAh), electrolysis was stopped and the electrolyte analyzed without isolation of 115ANi (crotyl) CNZnBr2. The substance yield was 65.8%. Current yield 42.7% (determined according to the voltamperogram).

Example XIX Ligand 115B -Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 25 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.45 g (0.55 mmol) 115B.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 76.5 mAh of electricity was passed through. The 0.45 g (0.55 mmol) ligand 115B was introduced after 30 mAh of electricity had been passed through. After 61.5 mAh of electricity had been passed through, the Ni anode was replaced with Zn and electrolysis continued. After dissolution of the Zn anode (surface area 4 cm2) (amount of electricity 15 mAh for formation of 0.5 equivalent M of ZnBr2), electrolysis was stopped and the electrolyte analyzed without isolation of 115BNi (crotyl) CNZnBr2.

The substance yield was 62.2%. Current yield 41.5% (determined according to the voltamperogram).

Example XX Ligand 115C Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 25 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.88 g (1.12 mmol) 115C.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 92.0 mAh of electricity was passed through. The 0.88 g (1.12 mmol) ligand 115C was introduced after 31 mAh of electricity had been passed through. After 61.0 mAh of electricity had been passed through, the nickel anode was replaced with zinc and electrolysis continued. After dissolution of the Zn anode (surface area 4 cm2) (amount of electricity 31 mAh for formation of 0.5 equivalent M of ZnBr2), electrolysis was stopped and the electrolyte analyzed without isolation of 115CNi (crotyl) CNZnBr2.

The substance yield and current yield were 67.8% (determined according to the voltamperogram).

Electrosynthesis of diphosphite nickel (0) complexes based on bis (naphthol) derivatives Ligand D5 Ligamd C As in the case of the bis (phosphite) ligands 115A, 115B and 115C, ligand D5 is sterically hindered and the complex (D5) 2Ni cannot be prepared for it. In Examples XXI-XXV, the production of D5Ni (3PN) x and D5Ni (crotyl) (CNZnBr2) complexes is demonstrated.

Example XXI Ligand D5 Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.5 g (0.53 mmol) D5.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 60 mAh of electricity was passed through. The 0.5 g (0.53 mmol) of ligand D5 was introduced after 30 mAh of electricity had been passed through. The D5Ni (3-PN) x complex was not isolated. The substance yield and current yield were 48.5% (determined according to the voltamperogram).

Example XXII Ligand D5 Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cor). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.5 g (0.53 mmol) D5.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 64 mAh of electricity was passed through. The 0.5 g (0.53 mmol) ligand D5 was introduced after 34 mAh of electricity had been passed through. The D5Ni (3-PN) x complex was not isolated. The substance yield was 56.6%. Current yield was 42.5% (determined according to the voltamperogram).

Example XXHI Ligand D5 Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged

to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.5 g (0.53 mmol) D5.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 104 mAh of electricity was passed through. The 0.5 g (0.53 mmol) of ligand D5 was introduced after 34 mAh of electricity had been passed through. The D5Ni (3-PN) X complex was not isolated. The substance yield 56.6%. Current yield 42.5% (determined according to the voltamperogram).

Example XXIV Ligand D5 Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 0.5 g (0.53 mmol) D5.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 112 mAh of electricity was passed through. The 0.5 g (0.53 mmol) of ligand D5 was introduced after 30 mAh of electricity had been passed through. After 30 mAh of electricity had been passed through, the nickel anode was replaced with Zn and the electrolysis continued. After dissolution of the Zn anode (surface area 5 cm2) (amount of electricity 82 mAh), electrolysis was stopped and the electrolyte analyzed without isolating the D5Ni (crotyl) CNZnBr2 complex. Substance yield was 58.2%. Current yield 33.6% (determined according to the voltamperogram).

Example XXV Ligand D5 Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, and 1.0 g (1.06 mmol) D5.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 326 mAh of electricity was passed through. The 1.0 g (1.06 mmol) of ligand D5 was introduced after 59 mAh of electricity had been passed through. After 59 mAh of electricity had been passed through, the Ni anode was replaced with Zn and the electrolysis continued. After dissolution of the Zn anode (surface area 5 cm2) (amount of electricity 267 mAh), electrolysis was stopped and the electrolyte analyzed without isolation of D5Ni (crotyl) CNZnBr2 complex. Substance yield was 76.1%. Current yield 38. 1% (determined according to the voltamperogram).

Example XXVI Ligand C Galvanostatic electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, 1.12 g (1.2 mmol) acac, and 1.6 g (1.2mmol) C.

The galvanostatic electrolysis was run at a current of 60 mA and 25°C. 98 mAh of electricity was passed through. The 1.6 g (2.9 mmol) of ligand C was introduced after 20 mAh of electricity had been passed through. 0.3 g NiC2 was isolated. Substance yield 54.8% (determined according to the voltamperogram).

Electrosynthesis of phosphite Ni (0) complexes, using alternating current Frequency of alternating current 50 Hz Example XXVII Preparative electrolysis was run in a glass diaphragmless electrolyzer (volume 50 mL) with a Ni anode in the form of a wire (surface area 5 cm2) and a nickel cathode in the form of a wire (surface area 5 cm2). The following were charged to the electrolyzer: 20 mL 3-PN, 0.6 g (1.86 mmol) Bu4NBr, 0.12 g (1.2 mmol) acac, and 2.0 g (5.7 mmol) p-TTP Electrolysis was run on a symmetric alternating current of 120 mA at 25°C.

234 mAh of electricity was passed through. 2.0 g (5.7 mmol) p-TTP ligand was

introduced after 36 mAh of electricity had been passed through. The complex Ni (p- TTP) 4 was not isolated. Substance yield was 39%. Current yield was 14.8% (determined according to the voltamperogram).

Example XXVIII Preparative electrolysis was run in a glass diaphragmless electrolyzer (volume 200 mL) with a Ni anode in the form of a 0.64 cm diameter rod and a copper cathode in the form of a wire. A silver wire reference electrode was used to control the anode voltage. The following were charged to the electrolyzer: 100 grams 3-PN, 11.703 grams of ligand V, 11.37 gr of ZnCl2,1. 394 gr of finely divided zinc powder. The ZnCl2 was used to increase the conductivity of the solution. The zinc was used to reduce the Ni+2 in solution to Ni (0) by the reaction: Ni [+2] (solution) + Zn [0] (suspended solid) + ligand ligand: Ni (0) + Zn [+2].

The ligand: Ni (0) is the active catalyst.

The Zn [+2] is then reduced at the cathode and plates out as Zn (0).

The zinc can be replaced with iron or any other reducing metal which is more electropositive than nickel. The reducing metal is preferably finely divided.

Electrolysis was run at a DC voltage of 1.8 volts (Vs the Ag electrode). The current was 10 to 20 milliamps. The solution temperature was controlled between 40 to 43° C. A dark orange color was observed after 392 coulombs. A sample taken after 560 coulombs of current indicated 0.025 wt% elemental nickel in solution as catalyst.

Total current passed through the solution was 672 coulombs. Current yield to active catalyst was 18%.

Although the invention has been described above in detail for the purpose of illustration, it is understood that the skilled artisan may make numerous variations and alterations without departing from the spirit and scope of the invention defined by the following claims.