Tetrakis(triphenyl phosphite)nickel(0)

[(PhO)3P]4Ni

[14221-00-2]  · C72H60NiO12P4  · Tetrakis(triphenyl phosphite)nickel(0)  · (MW 1299.89)

(catalyst for alkene and alkyne hydrocyanation1; styrene dimerization2)

Physical Data: mp 145 °C (dec).

Solubility: sol THF, toluene.

Form Supplied in: commercially available solid.

Preparative Methods: can be prepared by treating Nickel(II) Acetylacetonate with Sodium Borohydride and Triphenyl Phosphite.3

Handling, Storage, and Precautions: is a cancer suspect agent; is air sensitive and should be handled using Schlenk or glove-box techniques.

Hydrocyanation of Alkenes and Alkynes.

Hydrocyanation of 1,3-cyclohexadiene is catalyzed by [(PhO)3P]4Ni (eq 1).1 Silylalkynes are hydrocyanated by [(PhO)3P]4Ni to give isomeric mixtures of a- and b-silylacrylonitriles.4 When the bulky Ph3Si substituent is employed, regiospecific formation of the b-silylacrylonitrile occurs (eq 2). Smaller silyl substituents and alkyl groups give increased amounts of the a-silyl isomer. Aminoalkynes and alkynols have also been hydrocyanated to similar mixtures of acrylonitriles.5,6

Styrene Dimerization.

[(PhO)3P]4Ni, in the presence of Trifluoroacetic Acid, catalyzes the dimerization of styrene (eq 3). The reaction forms only the linear dimer with (E):(Z) = 5.4.


1. Andell, O. S.; Baeckvall, J. E.; Moberg, C. ACS 1986, B40, 184.
2. Fitzmaurice, N. J.; Jackson, W. R.; Perlmutter, P. JOM 1985, 285, 375.
3. McLaughlin, J. R. Inorg. Nucl. Chem. Lett. 1973, 9, 565.
4. Sakakibara, Y.; Umehara, S.; Sakai, M.; Uchino, N. NKK 1982, 818.
5. Jackson, W. R.; Perlmutter, P.; Smallridge, A. J. AJC 1988, 41, 1201.
6. Jackson, W. R.; Lovel, C. G.; Perlmutter, P.; Smallridge, A. J. AJC 1988, 41, 1099.

Gregory T. Whiteker

Union Carbide Corporation, South Charleston, WV, USA



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