MACROCYCLES INCORPORATING SULFUR AND NIDO-CARBORANE CAGES - REACTIVITY TOWARD NICKEL(II) AND PALLADIUM(II) - MOLECULAR-STRUCTURES OF PD(7,8-MU-(S(CH2CH2OCH2CH2OCH2CH2OCH2CH2)S)C2B9H10)2 AND PD(P(C6H5)3)CL(7,8-MU-(SCH2CH2S)C2B9H10)

The reactions of exo-dithio-7,8-dicarba-nido-undecaborate derivatives with Ni(II) and Pd(II) chlorides and phosphine chloride complexes are presented and discussed. Three different stoichiometries have been observed, [MLCl2]-, [M2L2Cl2], and [ML2]. The capacity of these ligands to act as tricoordinating agents through the two sulfur atoms and a B(3)-H --> M bond is introduced and discussed. A regularity in the value of the dihedral angle-omega (planes defined by S-M-S and S-C(c)-C(c)-S) and the length of the exo-cluster chain has been observed. The shorter the exo-cluster chain is, the smaller the omega-angle. The molecular structures of Pd{7,8-mu-(S(CH2CH2OCH2CH2OCH2CH2OCH2CH2)S)C2B9H10}2 and Pd{P(C6H5)3}Cl{7,8-mu-(SCH2CH2S)C2B9H10} have been determined. The former crystallizes in space group P2(1)/c with 2 formula units per cell. The cell dimensions are a = 8.140 (2) angstrom, b = 20.083 (8) angstrom, c = 11.953 (3) angstrom, and beta = 104.09 (2)degrees. The latter crystallizes in space group P2(1)/n with 4 formula units per cell. The cell dimensions are a = 13.424 (2) angstrom, b = 10.315 (2) angstrom, c = 20.008 (4) angstrom, and beta = 90.83 (1)degrees.