PREPARATION AND CHARACTERIZATION OF COBALT(III), NICKEL(II), AND COPPER(I) COMPLEXES CONTAINING 5,8-DIPHENYL-5,8-DIPHOSPHA-2,11-DITHIADODECANE (L), CH3SCH2CH2P(C6H5)CH2CH2P(C6H5)CH2CH2SCH3, AND MOLECULAR-STRUCTURE OF [NI(RAC(P)-L)2](BF4)2

DELTA-RR,LAMBDA-SS-[Co(acac)2(rac(P)-L)]+ and [Co(acac)2(meso(P)-L)]+ were obtained by reaction of [Co(acac)3] (acac = 2,4-pentanedionate ion) with 5,8-diphenyl-5,8-diphospha-2,11-dithiadodecane (L) in 1:1 molar ratio in dichloromethane in the presence of active charcoal, no DELTA-SS,LAMBDA-RR isomer of the rac(P)-L complex being formed. Five-coordinate [Ni(rac(P)-L)2]2+ and [Ni(meso(P)-L)2]2+ were yielded by reaction of Ni(II) and L in 1:2 molar ratio in methanol, and the molecular structure of less soluble [Ni(rac(P)-L)2](BF4)2 was determined by X-ray analysis. Crystal data: monoclinic, space group P2(1)/n, a = 17.136(3), b = 20.134(5), c = 14.106(3) angstrom, beta = 93.30(2)-degrees, V = 4859(2) angstrom 3, Z = 4, R = 0.089 for 8001 reflections. The Ni atom is surrounded square pyramidally by four P atoms in the basal plane and one S atom at the apical position with distances of the Ni-P: 2.214(2)-2.234(2) angstrom and the Ni-S: 2.603(2) angstrom. Both [Ni(rac(P)-L)2]2+ and [Ni(meso(P)-L)2]2+ in CH2Cl2 solutions exchange four -SCH3 groups at the apical positin on the NMR time scale. White [Cu(rac(P)-L)]BF4 was precipitated selectively by reaction of Cu(BF4)2.6H2O and L in 1:1 molar ratio in ethanol.