Issue 12, 2021

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

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].

Graphical abstract: Synthesis, properties and structural features of molybdenum(v) oxide trichloride complexes with neutral chalcogenoether ligands

Supplementary files

Article information

Article type
Paper
Submitted
05 1 2021
Accepted
26 2 2021
First published
03 3 2021
This article is Open Access
Creative Commons BY license

Dalton Trans., 2021,50, 4380-4389

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

D. E. Smith, W. Levason, J. Powell and G. Reid, Dalton Trans., 2021, 50, 4380 DOI: 10.1039/D1DT00038A

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