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Synthesis, properties and structural features of molybdenum(V) oxide trichloride complexes with neutral chalcogenoether ligands

Synthesis, properties and structural features of molybdenum(V) oxide trichloride complexes with neutral chalcogenoether ligands
Synthesis, properties and structural features of molybdenum(V) oxide trichloride complexes with neutral chalcogenoether ligands
Complexes of oxotrichloromolybdenum(V) with neutral group 16 donor ligands, [MoOCl3(L–L)] (L–L = RS(CH2)2SR, R = iPr, Ph; MeS(CH2)3SMe; MeSe(CH2)2SeMe; MeSe(CH2)3SeMe), [{MoOCl2(EMe2)}2(μ-Cl)2] (E = S, Se, Te), [(MoOCl3)2{o-C6H4(EMe)2}]n (E = Se or Te) and [(MoOCl3)2{MeTe(CH2)3TeMe}]n, have been obtained by reaction of the ligands with [MoOCl3(thf)2] or MoOCl3 in either CH2Cl2 or toluene, and characterised by microanalysis, IR and UV-visible spectroscopy and magnetic measurements. The telluroethers are the first examples containing Mo in a positive oxidation state. X-ray crystal structures are reported for the six-coordinate fac-[MoOCl3{MeS(CH2)3SMe}], mer-[MoOCl3{iPrS(CH2)2SiPr}] and mer-[MoOCl3{MeSe(CH2)2SeMe}], as well as the six-coordinate chloride-bridged dimers, [{MoOCl2(SMe2)}2(μ-Cl)2] and [{MoOCl2(SeMe2)}2(μ-Cl)2]. The structure of the mixed-valence decomposition product, [MoIVCl{o-C6H4(TeMe)2}2(μ-O)MoVOCl4], was also determined. In toluene solution MoOCl4 is reduced by MeS(CH2)3SMe to produce the Mo(V) complex, [MoOCl3{ MeS(CH2)3SMe}]. Crystal structures of the previously unknown diphosphine analogue, [MoOCl3{Me2P(CH2)2PMe2}], and the mixed-valence derivative [MoIVCl{Me2P(CH2)2PMe2}2(μ-O)MoVOCl4] are also reported for comparison and help to clarify earlier contradictory literature reports. In contrast to the dimeric EMe2 complexes, [{MoOCl2(EMe2)}2(μ-Cl)2], PMe3 forms the monomeric complex, fac-[MoOCl3(PMe3)2].
0300-9246
4380-4389
Smith, Danielle E.
aae55f94-b99a-4e9f-9d1b-8bcd3f2a93b6
Levason, William
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Powell, James
7f792402-08ab-4210-8d09-a43e31f83783
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Smith, Danielle E.
aae55f94-b99a-4e9f-9d1b-8bcd3f2a93b6
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Powell, James
7f792402-08ab-4210-8d09-a43e31f83783
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Smith, Danielle E., Levason, William, Powell, James and Reid, Gillian (2021) Synthesis, properties and structural features of molybdenum(V) oxide trichloride complexes with neutral chalcogenoether ligands. Dalton Transactions, 50 (12), 4380-4389. (doi:10.1039/D1DT00038A).

Record type: Article

Abstract

Complexes of oxotrichloromolybdenum(V) with neutral group 16 donor ligands, [MoOCl3(L–L)] (L–L = RS(CH2)2SR, R = iPr, Ph; MeS(CH2)3SMe; MeSe(CH2)2SeMe; MeSe(CH2)3SeMe), [{MoOCl2(EMe2)}2(μ-Cl)2] (E = S, Se, Te), [(MoOCl3)2{o-C6H4(EMe)2}]n (E = Se or Te) and [(MoOCl3)2{MeTe(CH2)3TeMe}]n, have been obtained by reaction of the ligands with [MoOCl3(thf)2] or MoOCl3 in either CH2Cl2 or toluene, and characterised by microanalysis, IR and UV-visible spectroscopy and magnetic measurements. The telluroethers are the first examples containing Mo in a positive oxidation state. X-ray crystal structures are reported for the six-coordinate fac-[MoOCl3{MeS(CH2)3SMe}], mer-[MoOCl3{iPrS(CH2)2SiPr}] and mer-[MoOCl3{MeSe(CH2)2SeMe}], as well as the six-coordinate chloride-bridged dimers, [{MoOCl2(SMe2)}2(μ-Cl)2] and [{MoOCl2(SeMe2)}2(μ-Cl)2]. The structure of the mixed-valence decomposition product, [MoIVCl{o-C6H4(TeMe)2}2(μ-O)MoVOCl4], was also determined. In toluene solution MoOCl4 is reduced by MeS(CH2)3SMe to produce the Mo(V) complex, [MoOCl3{ MeS(CH2)3SMe}]. Crystal structures of the previously unknown diphosphine analogue, [MoOCl3{Me2P(CH2)2PMe2}], and the mixed-valence derivative [MoIVCl{Me2P(CH2)2PMe2}2(μ-O)MoVOCl4] are also reported for comparison and help to clarify earlier contradictory literature reports. In contrast to the dimeric EMe2 complexes, [{MoOCl2(EMe2)}2(μ-Cl)2], PMe3 forms the monomeric complex, fac-[MoOCl3(PMe3)2].

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MoOCl3 chalcogenoether paper - final version revised 14_2_21 - no highlighting - Accepted Manuscript
Available under License University of Southampton Accepted Manuscript Licence.
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Accepted/In Press date: 26 February 2021
e-pub ahead of print date: 3 March 2021
Published date: 3 March 2021
Additional Information: Funding Information: We thank the EPSRC for support (EP/P025137/1) and for a studentship to D. E. S. (EP/N509747/1). Publisher Copyright: © The Royal Society of Chemistry 2021. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
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Identifiers

Local EPrints ID: 447852
URI: http://eprints.soton.ac.uk/id/eprint/447852
DOI: doi:10.1039/D1DT00038A
ISSN: 0300-9246
PURE UUID: 6ca451ac-cefd-456b-bb10-cb6eec2931d5
ORCID for Danielle E. Smith: ORCID iD orcid.org/0000-0002-2446-1763
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 24 Mar 2021 18:30
Last modified: 28 Aug 2024 02:00

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Author: Danielle E. Smith ORCID iD
Author: William Levason ORCID iD
Author: James Powell
Author: Gillian Reid ORCID iD

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