The reactions of MoOCl4 with neutral Group 15 and 16 ligands and a re-investigation of some N-donor ligand complexes of MoOCl3
The reactions of MoOCl4 with neutral Group 15 and 16 ligands and a re-investigation of some N-donor ligand complexes of MoOCl3
The reaction of molybdenum(VI) oxide tetrachloride, MoOCl4, with neutral ligands including MeCN, Ph3PO, SMe2, MeS(CH2)3SMe, SeMe2, PMe3, 2,2’-bipyridyl and 1,10-phenanthroline, results in reduction to form oxomolybdenum(V) complexes, identified by microanalysis, IR and UV/visible spectroscopy and via X-ray crystal structure analyses of several examples. Unexpectedly, the product formed with SeMe2 was [SeMe3]2[Mo2O2Cl6(μ-Cl)2] and with SMe2, [SMe2Cl]2[Mo2O2Cl6(μ-Cl)2]. X-ray crystal structures are reported for mer-[MoOCl3(MeCN)2], [{MoOCl2(MeCN)}2(µ-Cl)2], [MoOCl3{MeS(CH2)3SMe}], [SeMe3][MoOCl4(H2O)], [SMe2Cl]2[Mo2O2Cl6(μ-Cl)2] and [PMe3H][MoOCl4(PMe3)]. The reaction of MoOCl4 with [Et4N]Cl forms the dinuclear Mo(V) species, [Et4N]2[Mo2O2Cl6(μ-Cl)2].
The red mer-[MoOCl3(diimine)] (diimine = 2,2’-bipyridyl, 1,10-phenathroline) complexes were prepared from [MoOCl3(thf)2] and the diimine and fully characterised by spectroscopy and by X-ray crystallography. The long-known ‘green isomers’ of [MoOCl3(diimine)] obtained from MoOCl4 and the diimines (and in other ways), are suggested to be the red isomers co-crystallised with another lower oxidation state molybdenum complex.
1, 10-phenanthroline, 2, 2’-bipyridyl, Molybdenum oxide tetrachloride, molybdenum oxide trichloride, x-ray structures
Greenacre, Victoria
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Levason, William
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Powell, James
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Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle E.
aae55f94-b99a-4e9f-9d1b-8bcd3f2a93b6
13 May 2021
Greenacre, Victoria
c665a38b-0b1a-4671-ac75-bf0679dd1c57
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Powell, James
7f792402-08ab-4210-8d09-a43e31f83783
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle E.
aae55f94-b99a-4e9f-9d1b-8bcd3f2a93b6
Greenacre, Victoria, Levason, William, Powell, James, Reid, Gillian and Smith, Danielle E.
(2021)
The reactions of MoOCl4 with neutral Group 15 and 16 ligands and a re-investigation of some N-donor ligand complexes of MoOCl3.
Polyhedron, 204, [115262].
(doi:10.1016/j.poly.2021.115262).
Abstract
The reaction of molybdenum(VI) oxide tetrachloride, MoOCl4, with neutral ligands including MeCN, Ph3PO, SMe2, MeS(CH2)3SMe, SeMe2, PMe3, 2,2’-bipyridyl and 1,10-phenanthroline, results in reduction to form oxomolybdenum(V) complexes, identified by microanalysis, IR and UV/visible spectroscopy and via X-ray crystal structure analyses of several examples. Unexpectedly, the product formed with SeMe2 was [SeMe3]2[Mo2O2Cl6(μ-Cl)2] and with SMe2, [SMe2Cl]2[Mo2O2Cl6(μ-Cl)2]. X-ray crystal structures are reported for mer-[MoOCl3(MeCN)2], [{MoOCl2(MeCN)}2(µ-Cl)2], [MoOCl3{MeS(CH2)3SMe}], [SeMe3][MoOCl4(H2O)], [SMe2Cl]2[Mo2O2Cl6(μ-Cl)2] and [PMe3H][MoOCl4(PMe3)]. The reaction of MoOCl4 with [Et4N]Cl forms the dinuclear Mo(V) species, [Et4N]2[Mo2O2Cl6(μ-Cl)2].
The red mer-[MoOCl3(diimine)] (diimine = 2,2’-bipyridyl, 1,10-phenathroline) complexes were prepared from [MoOCl3(thf)2] and the diimine and fully characterised by spectroscopy and by X-ray crystallography. The long-known ‘green isomers’ of [MoOCl3(diimine)] obtained from MoOCl4 and the diimines (and in other ways), are suggested to be the red isomers co-crystallised with another lower oxidation state molybdenum complex.
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MoOCl3 MoOCl4 final revised 03_05_21 clear version
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Accepted/In Press date: 5 May 2021
e-pub ahead of print date: 13 May 2021
Published date: 13 May 2021
Additional Information:
Funding Information:
We thank EPSRC for support via EP/P025137/1 and EP/N509747/1.
Publisher Copyright:
© 2021 Elsevier Ltd
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Copyright 2021 Elsevier B.V., All rights reserved.
Keywords:
1, 10-phenanthroline, 2, 2’-bipyridyl, Molybdenum oxide tetrachloride, molybdenum oxide trichloride, x-ray structures
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Local EPrints ID: 449411
URI: http://eprints.soton.ac.uk/id/eprint/449411
ISSN: 0277-5387
PURE UUID: a094eae4-caee-419f-9a8c-4d994cbfd3da
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Date deposited: 27 May 2021 16:31
Last modified: 28 Aug 2024 04:01
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Author:
Victoria Greenacre
Author:
James Powell
Author:
Danielle E. Smith
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