Phosphine and phosphido indium hydride complexes and their use in inorganic synthesis

Abstract

Reaction of PR₃, R = cyclohexyl (Cy), cyclopentyl (Cy^p) or phenyl, with [InH₃(NMe₃)] affords the 1∶1 indium trihydride complexes, [InH₃(PR₃)]. The stabilities and spectroscopic properties of these complexes are described in terms of the phosphine ligands’ steric bulk and nucleophilicity. Reaction of two equivalents of PCy₃ with [InH₃(NMe₃)] yields the complex [InH₃(PCy₃)₂] which has been characterised by X-ray crystallography. The first phosphido–indium hydride complex, [{InH₂(PCy₂)}₃], has been prepared by a novel synthetic route which involves treatment of [InH₃(NMe₃)] with LiPCy₂. Its crystal structure shows it to exist as a cyclic trimer in the solid state. The complex, [InH₃(PCy₃)] has been used to prepare a range of monomeric indium chalcogenolato complexes, [In(EPh)₃(PCy₃)], E = S, Se or Te, all of which have been structurally characterised.