Smith Danielle E, Levason William, Powell James, Reid Gillian
School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK.
Dalton Trans. 2021 Mar 28;50(12):4380-4389. doi: 10.1039/d1dt00038a. Epub 2021 Mar 11.
Complexes of oxotrichloromolybdenum(v) with neutral group 16 donor ligands, [MoOCl(L-L)] (L-L = RS(CH)SR, R = Pr, Ph; MeS(CH)SMe; MeSe(CH)SeMe; MeSe(CH)SeMe), [{MoOCl(EMe)}(μ-Cl)] (E = S, Se, Te), [(MoOCl){o-CH(EMe)}] (E = Se or Te) and [(MoOCl){MeTe(CH)TeMe}], have been obtained by reaction of the ligands with [MoOCl(thf)] or MoOCl in either CHCl 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-[MoOCl{MeS(CH)SMe}], mer-[MoOCl{PrS(CH)SPr}] and mer-[MoOCl{MeSe(CH)SeMe}], as well as the six-coordinate chloride-bridged dimers, [{MoOCl(SMe)}(μ-Cl)] and [{MoOCl(SeMe)}(μ-Cl)]. The structure of the mixed-valence decomposition product, [MoCl{o-CH(TeMe)}(μ-O)MoOCl], was also determined. In toluene solution MoOCl is reduced by MeS(CH)SMe to produce the Mo(v) complex, [MoOCl{ MeS(CH)SMe}]. Crystal structures of the previously unknown diphosphine analogue, [MoOCl{MeP(CH)PMe}], and the mixed-valence derivative [MoCl{MeP(CH)PMe}(μ-O)MoOCl] are also reported for comparison and help to clarify earlier contradictory literature reports. In contrast to the dimeric EMe complexes, [{MoOCl(EMe)}(μ-Cl)], PMe forms the monomeric complex, fac-[MoOCl(PMe)].
氧代三氯钼（Ⅴ）与中性第16族供体配体的配合物，[MoOCl(L-L)]（L-L = RS(CH)SR，R = Pr、Ph；MeS(CH)SMe；MeSe(CH)SeMe；MeSe(CH)SeMe），[{MoOCl(EMe)}(μ-Cl)]（E = S、Se、Te），[(MoOCl){o-CH(EMe)}]（E = Se或Te）以及[(MoOCl){MeTe(CH)TeMe}]，是通过配体与[MoOCl(thf)]或MoOCl在CHCl₃或甲苯中反应得到的，并通过微量分析、红外光谱和紫外可见光谱以及磁性测量进行了表征。碲醚是首例含有处于正氧化态钼的化合物。报道了六配位面式-[MoOCl{MeS(CH)SMe}]、 merid-[MoOCl{PrS(CH)SPr}]和merid-[MoOCl{MeSe(CH)SeMe}]以及六配位氯桥联二聚体[{MoOCl(SMe)}(μ-Cl)]和[{MoOCl(SeMe)}(μ-Cl)]的X射线晶体结构。还测定了混合价态分解产物[MoCl{o-CH(TeMe)}(μ-O)MoOCl]的结构。在甲苯溶液中，MoOCl被MeS(CH)SMe还原生成钼（Ⅴ）配合物[MoOCl{MeS(CH)SMe}]。还报道了此前未知的二膦类似物[MoOCl{MeP(CH)PMe}]以及混合价态衍生物[MoCl{MeP(CH)PMe}(μ-O)MoOCl]的晶体结构，用于比较并有助于澄清早期相互矛盾的文献报道。与二聚体EMe配合物[{MoOCl(EMe)}(μ-Cl)]不同，PMe形成单体配合物面式-[MoOCl(PMe)]。
