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Synthesis, spectroscopic and structural systematics of complexes of germanium(IV) halides (GeX4, X = F, Cl, Br or I) with phosphane oxides and related oxygen donor ligands

Synthesis, spectroscopic and structural systematics of complexes of germanium(IV) halides (GeX4, X = F, Cl, Br or I) with phosphane oxides and related oxygen donor ligands
Synthesis, spectroscopic and structural systematics of complexes of germanium(IV) halides (GeX4, X = F, Cl, Br or I) with phosphane oxides and related oxygen donor ligands
The first series of phosphane oxide complexes of germanium(IV) halides have been prepared, including trans-[GeF4(R3PO)2] (R = Me, Et or Ph), trans-[GeCl4(Et3PO)2], fac-[GeCl3(Me3PO)3]2[GeCl6] and cis-[GeX2(Me3PO)4]X2 (X = Cl or Br) and characterised by IR and multinuclear NMR (1H, 19F{1H} and 31P{1H}) spectroscopy. Crystal structures of all the above (except trans-[GeCl4(Et3PO)2]) are described. Remarkably, under mild conditions Me3PO displaces halide ligands from GeX4 (X = Cl, Br) to form the cationic species above. Ph3AsO forms trans-[GeF4(Ph3AsO)2], but reaction of Ph3AsO or Me3AsO with GeCl4 leads to the corresponding R3AsCl2. The complexes [GeF4(MeCN)2], [GeF4(thf)2] and [GeF4(MeOCH2CH2OMe)] are also described and the relative Lewis acidities of GeX4 established.
crystal-structures, dichloride, trimethylphosphine oxide, triphenylarsine oxide, phosphane oxides, germanium, example, phosphorus, infrared spectra, coordination complexes
1434-1948
2488-2495
Cheng, F.
5efb5dbd-d284-4e80-a3f7-5cffb3ff24fb
Davis, M.F.
22d05b77-e973-4ca6-9148-bf63a99c6316
Hector, A.L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, M.
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, W.J.
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Cheng, F.
5efb5dbd-d284-4e80-a3f7-5cffb3ff24fb
Davis, M.F.
22d05b77-e973-4ca6-9148-bf63a99c6316
Hector, A.L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, W.
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, G.
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, M.
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, W.J.
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Cheng, F., Davis, M.F., Hector, A.L., Levason, W., Reid, G., Webster, M. and Zhang, W.J. (2007) Synthesis, spectroscopic and structural systematics of complexes of germanium(IV) halides (GeX4, X = F, Cl, Br or I) with phosphane oxides and related oxygen donor ligands. European Journal of Inorganic Chemistry, (17), 2488-2495. (doi:10.1002/ejic.200700233).

Record type: Article

Abstract

The first series of phosphane oxide complexes of germanium(IV) halides have been prepared, including trans-[GeF4(R3PO)2] (R = Me, Et or Ph), trans-[GeCl4(Et3PO)2], fac-[GeCl3(Me3PO)3]2[GeCl6] and cis-[GeX2(Me3PO)4]X2 (X = Cl or Br) and characterised by IR and multinuclear NMR (1H, 19F{1H} and 31P{1H}) spectroscopy. Crystal structures of all the above (except trans-[GeCl4(Et3PO)2]) are described. Remarkably, under mild conditions Me3PO displaces halide ligands from GeX4 (X = Cl, Br) to form the cationic species above. Ph3AsO forms trans-[GeF4(Ph3AsO)2], but reaction of Ph3AsO or Me3AsO with GeCl4 leads to the corresponding R3AsCl2. The complexes [GeF4(MeCN)2], [GeF4(thf)2] and [GeF4(MeOCH2CH2OMe)] are also described and the relative Lewis acidities of GeX4 established.

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Published date: 2007
Keywords: crystal-structures, dichloride, trimethylphosphine oxide, triphenylarsine oxide, phosphane oxides, germanium, example, phosphorus, infrared spectra, coordination complexes

Identifiers

Local EPrints ID: 54264
URI: http://eprints.soton.ac.uk/id/eprint/54264
ISSN: 1434-1948
PURE UUID: 00de973f-0c24-4753-a13a-1892b6650f5f
ORCID for A.L. Hector: ORCID iD orcid.org/0000-0002-9964-2163
ORCID for W. Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for G. Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 31 Jul 2008
Last modified: 16 Mar 2024 02:53

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Contributors

Author: F. Cheng
Author: M.F. Davis
Author: A.L. Hector ORCID iD
Author: W. Levason ORCID iD
Author: G. Reid ORCID iD
Author: M. Webster
Author: W.J. Zhang

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