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Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands

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
0277-5387
1-6
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle, Emily
dca4b149-33c4-4bc6-9f67-3d46b862363c
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle, Emily
dca4b149-33c4-4bc6-9f67-3d46b862363c
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Levason, William, Reid, Gillian, Smith, Danielle, Emily and Zhang, Wenjian (2020) Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands. Polyhedron, 179, 1-6, [114372]. (doi:10.1016/j.poly.2020.114372).

Record type: Article

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].

Text
Tungsten Arsine Phosphines final revised 12_01_20 - accepted - Accepted Manuscript
Restricted to Repository staff only until 14 January 2022.
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Text
Appendix A Polyhedron - final accepted
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More information

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
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468
ORCID for Danielle, Emily Smith: ORCID iD orcid.org/0000-0002-2446-1763

Catalogue record

Date deposited: 06 Feb 2020 17:32
Last modified: 18 Feb 2021 17:32

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