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. Can. J. Chem. 68, 628 (1990). The disproportionation of the complex (Et2N)3Ti(pPCy2)Ni(PPh3) affords the coordinatively unsaturated species Ni(PPh3)3, 1. This compound crystallizes in the triclinic space group P1, with a = 18.483(4) A, b = 16.203(3) A, c = 17.783(4) A, a = 105.85(2)", P = 117.33(3)", y = 92.33(3)", Z = 4, and V = 4464(2) A3. Full-matrix least-squares refinement of 1042 variables using 6484 data ( F: > 3uF: ) gave R = 0.0441 and R , = 0.0438. The two crystallographically independent molecules are essentially identical, each exhibiting a trigonal planar coordination sphere at Ni. The most interesting feature of the structure is the close approach (2.744-3.094 A) of three ortho hydrogens of the PPh3 groups to the Ni centres. The implications of the structural data regarding ortho metallation and the known instability of 1 are discussed. On discute des implications des donnkes de la structure sur la mktallation en ortho et sur l'instabilite bien connue du compose.Mots clis : non-saturk d'un point de vue de la coordination, complexe du nickel avec des phosphines.[Traduit par la revue]

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Organoaluminum and -gallium thiolates are prepared in high yield by the reaction of triorganoaluminum and -gallium derivatives with thiols. In this way, [Mes2Al(M-SBz)]2 (Mes = 2,4,6-Me3C6H2 8), and {Me2Ga[w-S(2,6-Me2CeH3)]}4 (9) were prepared and crystallographically characterized. The dimethyl-and dimesitylaluminum thiolates 1-3 were determined to be dimeric with four-membered (A1S)2 rings. The structure of 1 was determined in space group P2i/n (No.