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Gallium(III) halide complexes with phosphines, arsines and phosphine oxides - a comparative study

Gallium(III) halide complexes with phosphines, arsines and phosphine oxides - a comparative study
Gallium(III) halide complexes with phosphines, arsines and phosphine oxides - a comparative study
The phosphine oxide complexes [GaX3(Me3PO)] and [(GaX3)2{?-o-C6H4(CH2P(O)Ph2)2}] have been prepared and characterised by microanalysis, IR and multinuclear NMR (1H, 13C{1H}, 31P{1H} and 71Ga) spectroscopy. The structures of [GaCl3(Me3PO)], [(GaBr3)2{?-o-C6H4(CH2P(O)Ph2)2}] and of the ionic product [GaI2(Me3PO)2][GaI4] have been determined and show that the Lewis acidity of the gallium halides towards phosphinoyl ligands diminishes as the halogen becomes heavier. The [GaX3(Ph3E)] (X = Cl, Br or I; E = P or As) and [(GaX3)2{?-o-C6H4(CH2PPh2)2}] (X = Br or I) have been prepared and their structural and spectroscopic properties compared with those of the phosphinoyl complexes. The results, and competitive solution NMR studies, show that Ga(III) binds the hard R3PO in preference to the softer phosphine or arsine ligands. Hydrolysis of gallium(III) phosphines is shown to lead to [R3PH][GaX4], but in contrast to some other p-block halides, GaX3 do not promote air-oxidation of R3P to R3PO.
gallium, diphosphine, thio-ether, adducts, structural-characterization, phosphonium, crystal-structures, magnetic-resonance, antimony(iii), phosphine oxide, seleno-ether ligands, nmr spectroscopy, tin(iv) halides, coordination complexes, phosphine
0277-5387
4147-4155
Cheng, F.
5efb5dbd-d284-4e80-a3f7-5cffb3ff24fb
Codgbrook, H.L.
59b51d27-e339-4048-a02d-0ca94ff685ff
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.
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Cheng, F.
5efb5dbd-d284-4e80-a3f7-5cffb3ff24fb
Codgbrook, H.L.
59b51d27-e339-4048-a02d-0ca94ff685ff
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.
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Cheng, F., Codgbrook, H.L., Hector, A.L., Levason, W., Reid, G., Webster, M. and Zhang, W. (2007) Gallium(III) halide complexes with phosphines, arsines and phosphine oxides - a comparative study. Polyhedron, 26 (15), 4147-4155. (doi:10.1016/j.poly.2007.05.008).

Record type: Article

Abstract

The phosphine oxide complexes [GaX3(Me3PO)] and [(GaX3)2{?-o-C6H4(CH2P(O)Ph2)2}] have been prepared and characterised by microanalysis, IR and multinuclear NMR (1H, 13C{1H}, 31P{1H} and 71Ga) spectroscopy. The structures of [GaCl3(Me3PO)], [(GaBr3)2{?-o-C6H4(CH2P(O)Ph2)2}] and of the ionic product [GaI2(Me3PO)2][GaI4] have been determined and show that the Lewis acidity of the gallium halides towards phosphinoyl ligands diminishes as the halogen becomes heavier. The [GaX3(Ph3E)] (X = Cl, Br or I; E = P or As) and [(GaX3)2{?-o-C6H4(CH2PPh2)2}] (X = Br or I) have been prepared and their structural and spectroscopic properties compared with those of the phosphinoyl complexes. The results, and competitive solution NMR studies, show that Ga(III) binds the hard R3PO in preference to the softer phosphine or arsine ligands. Hydrolysis of gallium(III) phosphines is shown to lead to [R3PH][GaX4], but in contrast to some other p-block halides, GaX3 do not promote air-oxidation of R3P to R3PO.

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More information

Published date: 2007
Keywords: gallium, diphosphine, thio-ether, adducts, structural-characterization, phosphonium, crystal-structures, magnetic-resonance, antimony(iii), phosphine oxide, seleno-ether ligands, nmr spectroscopy, tin(iv) halides, coordination complexes, phosphine
Organisations: Chemistry

Identifiers

Local EPrints ID: 145977
URI: https://eprints.soton.ac.uk/id/eprint/145977
ISSN: 0277-5387
PURE UUID: 2fc65ca2-691f-44f7-afa9-7900c6e2b2c4
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: 07 Jun 2010 09:12
Last modified: 20 Jul 2019 01:28

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