Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of indium(III) halides

The ligands o-C6H4(PMe2)2 and o-C6H4(AsMe2)2 (L?L) react with anhydrous InX3 (X = Cl, Br, or I) in a 2:1 InX3/ligand ratio to form [InX2(L?L)][InX4] containing distorted tetrahedral cations, established by X-ray crystal structures for L?L = o-C6H4(PMe2)2 (X = Br or I) and o-C6H4(AsMe2)2 (X = I). IR, Raman, and multinuclear NMR (1H, 31P, 115In) spectroscopy show that these are the only species present in solution in chlorocarbons and in the bulk solids. The products from reactions in a 1:1 or 1:2 molar ratio are more diverse and include the halide-bridged dimers [In2Cl6{o-C6H4(PMe2)2}2] and [In2X6{o-C6H4(AsMe2)2}2] (X = Cl or Br) and the distorted octahedral cation trans-[InBr2{o-C6H4(PMe2)2}2][InBr4]. The neutral complexes partially rearrange in chlorocarbon solution, with multinuclear NMR spectroscopy revealing [InX4]? among other species. The iodo complexes trans-[InI2(L?L)2][InI4(L?L)] contain rare examples of six-coordinate anions, as authenticated by an X-ray crystal structure for L?L = o-C6H4(PMe2)2. Two species of formula [In2Cl5(L?L)2]n[InCl4]n (L?L = o-C6H4(PMe2)2 and o-C6H4(AsMe2)2) were identified crystallographically and contain polymeric cations with six-coordinate indium centers bonded to one chelating L?L and a terminal chlorine, linked by alternating single and double chlorine bridges into chains. The complicated chemistry of InX3 with these two rigid chelates is contrasted with that of the flexible diphosphane Et2P(CH2)2PEt2, which forms [In2Cl6{Et2P(CH2)2PEt2}2], and with more sterically demanding o-C6H4(PPh2)2 (Sigl et al. Eur. J. Inorg. Chem. 1998, 203?210). The results also contrasted with those found for GaX3 with the same ligand