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Complexes of germanium(iv) fluoride with phosphane ligands: structural and spectroscopic authentication of germanium(iv) phosphane complexes

Complexes of germanium(iv) fluoride with phosphane ligands: structural and spectroscopic authentication of germanium(iv) phosphane complexes
Complexes of germanium(iv) fluoride with phosphane ligands: structural and spectroscopic authentication of germanium(iv) phosphane complexes
The first phosphane complexes of germanium(IV) fluoride, trans-[GeF4(PR3)2] (R = Me or Ph) and cis-[GeF4(diphosphane)] (diphosphane = R2P(CH2)2PR2, R = Me, Et, Ph or Cy; o-C6H4(PR2)2, R = Me or Ph) have been prepared from [GeF4(MeCN)2] and the ligands in dry CH2Cl2 and characterised by microanalysis, IR, Raman, 1H, 19F{1H} and 31P{1H} NMR spectroscopy. The crystal structures of [GeF4(diphosphane)] (diphosphane = Ph2P(CH2)2PPh2 and o-C6H4(PMe2)2) have been determined and show the expected cis octahedral geometries. In anhydrous CH2Cl2 solution the complexes are slowly converted into the corresponding phosphane oxide adducts by dry O2. The apparently contradictory literature on the reaction of GeCl4 with phosphanes is clarified. The complexes trans-[GeCl4(AsR3)2] (R = Me or Et) are obtained from GeCl4 and AsR3 either without solvent or in CH2Cl2, and the structures of trans-[GeCl4(AsEt3)2] and Et3AsCl2 determined. Unexpectedly, the complexes of GeF4 with arsane ligands are very unstable and have not been isolated in a pure state. The behaviour of the germanium(IV) halides towards phosphane and arsane ligands are compared with the corresponding silicon(IV) and tin(IV) systems.
0300-9246
2261-2269
Davis, Martin F.
72f26f03-4bbe-482e-b8a5-6c792b22fcc3
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Davis, Martin F.
72f26f03-4bbe-482e-b8a5-6c792b22fcc3
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7

Davis, Martin F., Levason, William, Reid, Gillian and Webster, Michael (2008) Complexes of germanium(iv) fluoride with phosphane ligands: structural and spectroscopic authentication of germanium(iv) phosphane complexes. Dalton Transactions, 17, 2261-2269. (doi:10.1039/b716765b).

Record type: Article

Abstract

The first phosphane complexes of germanium(IV) fluoride, trans-[GeF4(PR3)2] (R = Me or Ph) and cis-[GeF4(diphosphane)] (diphosphane = R2P(CH2)2PR2, R = Me, Et, Ph or Cy; o-C6H4(PR2)2, R = Me or Ph) have been prepared from [GeF4(MeCN)2] and the ligands in dry CH2Cl2 and characterised by microanalysis, IR, Raman, 1H, 19F{1H} and 31P{1H} NMR spectroscopy. The crystal structures of [GeF4(diphosphane)] (diphosphane = Ph2P(CH2)2PPh2 and o-C6H4(PMe2)2) have been determined and show the expected cis octahedral geometries. In anhydrous CH2Cl2 solution the complexes are slowly converted into the corresponding phosphane oxide adducts by dry O2. The apparently contradictory literature on the reaction of GeCl4 with phosphanes is clarified. The complexes trans-[GeCl4(AsR3)2] (R = Me or Et) are obtained from GeCl4 and AsR3 either without solvent or in CH2Cl2, and the structures of trans-[GeCl4(AsEt3)2] and Et3AsCl2 determined. Unexpectedly, the complexes of GeF4 with arsane ligands are very unstable and have not been isolated in a pure state. The behaviour of the germanium(IV) halides towards phosphane and arsane ligands are compared with the corresponding silicon(IV) and tin(IV) systems.

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e-pub ahead of print date: 19 March 2008
Published date: May 2008
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 146963
URI: http://eprints.soton.ac.uk/id/eprint/146963
ISSN: 0300-9246
PURE UUID: 9d57eae5-30f3-4757-bb6e-7f9af4f7fea9
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 23 Apr 2010 08:34
Last modified: 03 Dec 2019 02:07

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