Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands
Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands
The seven-coordinate tungsten(VI) complexes, [WOCl4{o-C6H4(EMe2)2}] and [WSCl4{o-C6H4(EMe2)2}] (E = P, As), have been prepared by reaction of WOCl4 or WSCl4 with the ligands in anhydrous CH2Cl2 or toluene, and fully characterised by microanalysis, IR, 1H and 31P{1H} NMR spectroscopy. The X-ray crystal structures of [WOCl4{o-C6H4(AsMe2)2}] and [WSCl4{o-C6H4(PMe2)2}] have been determined and revealed pentagonal bipyramidal geometries with axial O/Cl or S/Cl. Attempts to isolate similar complexes with o-C6H4(PPh2)2, PMe3 or AsEt3 were unsuccessful, due to facile reduction of the tungsten centre. Several reduction products have also been identified crystallographically, including the tungsten(V) species, [WOCl3{o-C6H4(PMe2)2}], WOCl3{o-C6H4(PMe2)(P(O)Me2)}] and [WCl4{o-C6H4(PPh2)2}2][WCl6].
Tungsten oxide tetrachloride, diarsine, diphosphine, x-ray structures
1-6
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle E.
aae55f94-b99a-4e9f-9d1b-8bcd3f2a93b6
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
15 March 2020
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle E.
aae55f94-b99a-4e9f-9d1b-8bcd3f2a93b6
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William, Reid, Gillian, Smith, Danielle E. and Zhang, Wenjian
(2020)
Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands.
Polyhedron, 179, , [114372].
(doi:10.1016/j.poly.2020.114372).
Abstract
The seven-coordinate tungsten(VI) complexes, [WOCl4{o-C6H4(EMe2)2}] and [WSCl4{o-C6H4(EMe2)2}] (E = P, As), have been prepared by reaction of WOCl4 or WSCl4 with the ligands in anhydrous CH2Cl2 or toluene, and fully characterised by microanalysis, IR, 1H and 31P{1H} NMR spectroscopy. The X-ray crystal structures of [WOCl4{o-C6H4(AsMe2)2}] and [WSCl4{o-C6H4(PMe2)2}] have been determined and revealed pentagonal bipyramidal geometries with axial O/Cl or S/Cl. Attempts to isolate similar complexes with o-C6H4(PPh2)2, PMe3 or AsEt3 were unsuccessful, due to facile reduction of the tungsten centre. Several reduction products have also been identified crystallographically, including the tungsten(V) species, [WOCl3{o-C6H4(PMe2)2}], WOCl3{o-C6H4(PMe2)(P(O)Me2)}] and [WCl4{o-C6H4(PPh2)2}2][WCl6].
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Tungsten Arsine Phosphines final revised 12_01_20 - accepted
- Accepted Manuscript
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Appendix A Polyhedron - final accepted
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Accepted/In Press date: 14 January 2020
e-pub ahead of print date: 18 January 2020
Published date: 15 March 2020
Keywords:
Tungsten oxide tetrachloride, diarsine, diphosphine, x-ray structures
Identifiers
Local EPrints ID: 437605
URI: http://eprints.soton.ac.uk/id/eprint/437605
ISSN: 0277-5387
PURE UUID: 75d19b62-14e1-4b79-a6b2-db185d7dece9
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Date deposited: 06 Feb 2020 17:32
Last modified: 17 Mar 2024 05:17
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Author:
Danielle E. Smith
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