Synthesis and characterization of indium compounds with phosphinothiol ligands. (see abstract)

Article abstract of DOI:10.1021/ic980282s

The electrochemical oxidation of anodic indium metal in an acetonitrile solution of phosphinothiol ligands affords [In{2-(Ph₂P)C₆H₄S}₃] (1), [In{2-(Ph₂P)-6-(Me₃Si)C₆H₃S)} ₂{2-(Ph₂PO)-6-(Me₃Si)C₆H ₃S}] (2), [In{2-(Ph₂PO)-6-(Me₃Si)C₆H₃S} ₃] (3), and [NMe₄][In{PhP(C₆H₄S-2)₂} ₂]·CH₃CN (4) complexes exhibiting distorted six-coordinate geometries based on {InS₃P₃}, {InS₃P₂O}, and {InS₄P₂} cores, respectively. In all cases, the In - P bond distances are anomalously long, presumably as a consequence of steric crowding. The anion of 4 provides an unusual example of an In(III)-thiolate coordination complex ion. Crystal data: 1, C₅₄H₄₂InP₃S₃, monoclinic, P2₁/c, a = 16.6579(1) A?, b = 12.6628(2) A?, c = 22.5520(3) A?, β = 96.42(1)°, V = 4727.15(1) A?³, Z = 4, 6176 reflections, R = 0.0579; 2, C₆₃H₆₆InOP₃S₃Si₃, monoclinic, P2₁/c, a = 11.53090(10) A?, b = 26.2505(3) A?, c = 20.4206(2) A?, β = 94.0870(10)°, V = 6165.43(11) A?³, Z = 4, 10 699 reflections, R = 0.0621; 4, C₄₂H₄₁InN₂P₂S₄, monoclinic, P2(1), a = 13.0052(2) A?, b = 11.2240(2) A?, c = 14.3070(3) A?, β= 93.190(1)°, V = 2085.16(7) A?³, Z = 2, 6651 reflections, R = 0.0352.