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DOI: 10.1039/A809541H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 1319-1324

Reaction of GeCl4 with some phosphorus and arsenic donor ligands; crystal structures of the germanium(II) complex [Bun3PCl][GeCl3] and the germanium(IV) complex GeCl4(AsMe3)2, the first reported example of a tertiary arsine complex of GeIV

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Stephen M. Godfrey, Imran Mushtaq and Robin G. Pritchard

Abstract

The tertiary phosphines PR3 {R3 = Me3, Et3, Prn3, Bun3, But3, (C6H11)3, [2,6-(CH3O)2C6H3]3, [2,4,6-(CH3O)3C6H2]3, (C6H5CH2)3, (Me2N)3, (Et2N)3, (Prn2N)3, Ph2Et or Ph3} and tertiary arsines AsR3 (R = Ph or Me) have been treated with germanium tetrachloride in both a 1∶1 and 2∶1 stoichiometric ratio in diethyl ether solution. In the tertiary phosphine reactions a redox reaction occurs to produce the ionic germanium(II) complexes [R3PCl][GeCl3] in near to quantitative yield, the chlorophosphinium cation being identified by 31P-{H} NMR spectroscopy. No evidence for the previously reported molecular germanium(IV) adducts GeCl4(PR3)2 was observed, apart from the possible assignments of minor peaks in the 31P-{H} NMR spectrum for some of the products. The crystal structure of [Bun3PCl][GeCl3] revealed no interaction between the cation and anion, in direct contrast to the only other reported complex of this stoichiometry, [Pri3PBr][GeBr3]. No reaction was observed between PPh3 and GeCl4. The reaction of AsMe3 with GeCl4 in both a 1∶1 and 2∶1 stoichiometric ratio produced the molecular trans-octahedral germanium(IV) complex, GeCl4(AsMe3)2, the first crystallographically characterised germanium(IV) tertiary arsine complex [d(Ge–As) = 2.472(1) Å]. No reaction occurred between GeCl4 and AsPh3.

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