The acid-base reactivity of MS2(dmpe)2, where M = Mo (1) and W (2) and dmpe = Me2PCH2CH2PMe 2, was examined. Compounds 1 and 2 arise via the one-pot reaction of (NH4)2MS4 and dmpe. Protonation of these species gives the stable salts [MS(SH)(dmpe)2]X. The pKa'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 Å to 2.06 and 2.57 Å, whereas the Mo-P distances do not change appreciably. 1H and 31P NMR studies for [1H]BArF4 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 H2S to afford [MoS(OTf)(dmpe)2]OTf, which forms an adduct with CD 3CN and regenerates 1 upon treatment with SH-/Et 3N solutions. Consistent with its ready protonation, complex 1 is methylated, and the use of excess MeOTf gives [MoS(OTf)(dmpe)2] + and Me2S in a rare example of double alkylation at a sulfido ligand.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry