Δ-RR,∧-SS-[Co(acac)2(rac(P)-L)]+ and [Co(acac)2(raeso(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 Δ-SS,∧-RR isomer of the rac(P)-L complex being formed. Five-coordinate [Ni(rac(P)-L)2]2+ and [Ni(raeso(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 P21/n, a=17.136(3), b=20.134(5), c=14.106(3) Å, β=93.30(2)°, V=4859(2) Å3, 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) Å and the Ni-S: 2.603(2) Å. 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.
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