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Complexes of WOCl4 and WSCl4 with neutral N- and O- donor ligands: synthesis, spectroscopy and structures

Complexes of WOCl4 and WSCl4 with neutral N- and O- donor ligands: synthesis, spectroscopy and structures
Complexes of WOCl4 and WSCl4 with neutral N- and O- donor ligands: synthesis, spectroscopy and structures
The complexes [WOCl4(L)] and [WSCl4(L)] (L = OPPh3, OPMe3, pyridine, 2,2’-bipyridyl), [{WOCl4}2(µ-L-L)] and [{WSCl4}2(µ-L-L)] (L-L = Ph2P(O)(CH2)nP(O)Ph2 (n = 1, 2)) have been prepared from WOCl4 or WSCl4 and the ligands in anhydrous CH2Cl2 solution, and characterised by microanalysis, IR and NMR (1H, 31P{1H}) spectroscopy. X-Ray crystal structures are reported for [WOCl4(OPPh3)], [{WOCl4}2(µ-Ph2P(O)(CH2)P(O)Ph2)] and [{WSCl4}2(µ-Ph2P(O)(CH2)2P(O)Ph2)]. All, except those of 2,2’-bipyridyl, are six-coordinate with the neutral donor trans to W=O or W=S. Spectroscopic data suggest that the [WOCl4(2,2’-bipy)] and [WSCl4(2,2’-bipy)] are seven-coordinate. Comparison of the structural and spectroscopic data for the two series of complexes indicate little difference in Lewis acidity between the two tungsten(VI) moieties. Decomposition of [WOCl4(OPMe3)] in solution gave the cyclic trimer [W3O3(µ-O)3Cl6(OPMe3)3], the structure of which revealed a six-membered W3O3 ring core with very asymmetric oxido-bridges. The structure of the tungsten(V) complex [WOCl3(2,2’-bipy)] is also reported.
Tungsten oxide tetrachloride, Tungsten sulfide tetrachloride, phosphine oxide, 2,2’-bipyridyl, x-ray structures
0277-5387
14-19
Greenacre, Victoria
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Hector, Andrew L.
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Levason, William
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Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle, Emily
dca4b149-33c4-4bc6-9f67-3d46b862363c
Sutcliffe, Laura
bd64753f-4f8e-4db6-8d1b-2c4a14e41a8e
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle, Emily
dca4b149-33c4-4bc6-9f67-3d46b862363c
Sutcliffe, Laura
bd64753f-4f8e-4db6-8d1b-2c4a14e41a8e

Greenacre, Victoria, Hector, Andrew L., Levason, William, Reid, Gillian, Smith, Danielle, Emily and Sutcliffe, Laura (2019) Complexes of WOCl4 and WSCl4 with neutral N- and O- donor ligands: synthesis, spectroscopy and structures. Polyhedron, 162, 14-19. (doi:10.1016/j.poly.2019.01.044).

Record type: Article

Abstract

The complexes [WOCl4(L)] and [WSCl4(L)] (L = OPPh3, OPMe3, pyridine, 2,2’-bipyridyl), [{WOCl4}2(µ-L-L)] and [{WSCl4}2(µ-L-L)] (L-L = Ph2P(O)(CH2)nP(O)Ph2 (n = 1, 2)) have been prepared from WOCl4 or WSCl4 and the ligands in anhydrous CH2Cl2 solution, and characterised by microanalysis, IR and NMR (1H, 31P{1H}) spectroscopy. X-Ray crystal structures are reported for [WOCl4(OPPh3)], [{WOCl4}2(µ-Ph2P(O)(CH2)P(O)Ph2)] and [{WSCl4}2(µ-Ph2P(O)(CH2)2P(O)Ph2)]. All, except those of 2,2’-bipyridyl, are six-coordinate with the neutral donor trans to W=O or W=S. Spectroscopic data suggest that the [WOCl4(2,2’-bipy)] and [WSCl4(2,2’-bipy)] are seven-coordinate. Comparison of the structural and spectroscopic data for the two series of complexes indicate little difference in Lewis acidity between the two tungsten(VI) moieties. Decomposition of [WOCl4(OPMe3)] in solution gave the cyclic trimer [W3O3(µ-O)3Cl6(OPMe3)3], the structure of which revealed a six-membered W3O3 ring core with very asymmetric oxido-bridges. The structure of the tungsten(V) complex [WOCl3(2,2’-bipy)] is also reported.

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Accepted/In Press date: 17 January 2019
e-pub ahead of print date: 25 January 2019
Published date: 1 April 2019
Keywords: Tungsten oxide tetrachloride, Tungsten sulfide tetrachloride, phosphine oxide, 2,2’-bipyridyl, x-ray structures

Identifiers

Local EPrints ID: 428124
URI: http://eprints.soton.ac.uk/id/eprint/428124
ISSN: 0277-5387
PURE UUID: 9d852564-9198-46e1-82a1-520ed68f63be
ORCID for Andrew L. Hector: ORCID iD orcid.org/0000-0002-9964-2163
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: 12 Feb 2019 17:30
Last modified: 18 Feb 2021 17:32

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Contributors

Author: Victoria Greenacre
Author: William Levason ORCID iD
Author: Gillian Reid ORCID iD
Author: Danielle, Emily Smith ORCID iD
Author: Laura Sutcliffe

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