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• W1986245904 endingPage "687" @default.
• W1986245904 startingPage "679" @default.
• W1986245904 abstract "The acid-base reactivity of MS(2)(dmpe)(2), where M = Mo (1) and W (2) and dmpe = Me(2)PCH(2)CH(2)PMe(2), was examined. Compounds 1 and 2 arise via the one-pot reaction of (NH(4))(2)MS(4) and dmpe. Protonation of these species gives the stable salts [MS(SH)(dmpe)(2)]X. The pK(a)'s of the Mo and W compounds are estimated to be 16.5 and 15.5, respectively. Protonation causes the M=S distances to diverge from 2.24 A to 2.06 and 2.57 A, whereas the Mo-P distances do not change appreciably. (1)H and (31)P NMR studies for [1H]BAr(F)(4) reveal that the proton exchange is competitive with the NMR time scale; at low temperatures, individual signals for both the parent disulfide and its conjugate acid can be observed. Treatment of 1 with excess HOTf liberates H(2)S to afford [MoS(OTf)(dmpe)(2)]OTf, which forms an adduct with CD(3)CN and regenerates 1 upon treatment with SH(-)/Et(3)N solutions. Consistent with its ready protonation, complex 1 is methylated, and the use of excess MeOTf gives [MoS(OTf)(dmpe)(2)](+) and Me(2)S in a rare example of double alkylation at a sulfido ligand." @default.
• W1986245904 created "2016-06-24" @default.
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• W1986245904 date "2005-12-23" @default.
• W1986245904 modified "2023-10-16" @default.
• W1986245904 title "MS₂(Me₂PC₂H₄PMe₂)₂ (M = Mo, W): Acid−Base Properties, Proton Transfer, and Reversible Protonolysis of Sulfido Ligands" @default.
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• W1986245904 doi "https://doi.org/10.1021/ic051443c" @default.
• W1986245904 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/16411703" @default.
• W1986245904 hasPublicationYear "2005" @default.
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