Diphosphine and diarsine complexes of germanium(II) halides—preparation, spectroscopic and structural studies

Cheng, Fei, Hector, Andrew L., Levason, William, Reid, Gillian, Webster, Michael and Zhang, Wenjian (2009) Diphosphine and diarsine complexes of germanium(II) halides—preparation, spectroscopic and structural studies. Inorganic Chemistry, 49 (2), 752-760. (doi:10.1021/ic902068z).

Abstract

The Ge(II) halide complexes [GeX2(L?L)] (L?L = o-C6H4(PPh2)2, o-C6H4(PMe2)2, Me2P(CH2)2PMe2; X = Cl, Br, I. L?L = Et2P(CH2)2PEt2; X = Cl or Br. L?L = o-C6H4(AsMe2)2; X = Br or I) and [GeCl(L?L)][GeCl3] (L?L = o-C6H4(AsMe2)2) have been prepared and characterized by IR, 1H and 31P{1H} NMR spectroscopy, and microanalyses. The crystal structures of [GeX2{o-C6H4(PPh2)2}] (X = Cl, Br, I) reveal discrete mononuclear units with a very asymmetric bidentate o-C6H4(PPh2)2 ligand and a bent GeX2 unit.

Those of [GeX2{o-C6H4(PMe2)2}] show symmetrically coordinated diphosphine with loosely associated dimer arrangements, formed through long Ge···X bridges between adjacent monomer units. [GeX2{R2P(CH2)2PR2}] (R = Me; X = Cl, Br, I. R = Et; X = Cl, Br) all show discrete monomer structures with 2-fold crystallographic symmetry and based upon four-coordinate Ge, with the diphosphine chelating and approximately linear GeX2 units. [GeI2{o-C6H4(AsMe2)2}] involves significant intermolecular Ge···I interactions, giving rise to a zigzag polymer chain.

Finally, the structure of [GeCl{o-C6H4(AsMe2)2}][GeCl3] shows pyramidal cations and anions both with crystallographic mirror symmetry, with the diarsine symmetrically chelating, and long Ge···Cl interactions give a loosely associated chain polymer with alternating cations and anions. Comparisons across this series of structurally diverse complexes are discussed.

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Contributors

Author: Andrew L. Hector

Author: William Levason

Author: Gillian Reid

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