17302-63-5Relevant articles and documents
Anion structure determination in the gas phase: Chemical reactivity as a probe
Lee, Jeehiun K.,Grabowski, Joseph J.
, p. 9422 - 9429 (2007/10/03)
In the gas phase, the discrimination between two isomeric anion structures is a challenge that requires different solutions for different applications. The anionic oxy-Cope rearrangement involves the rearrangement of an alkoxide to an isomeric enolate; the mechanistic study of such a process in the gas phase requires a simple and selective probe process. Using a flowing afterglow mass spectrometer, we have examined the utility and limitations of using chemical reactivity to discriminate between alkoxides and enolates in the gas phase. A series of alkoxides and enolates were allowed to react with three chemical probe reagents: methanol-O-d, methyl nitrite, and dimethyl disulfide. Quantitative and qualitative characterization of each probe reagent reveals the especially broad and flexible utility of dimethyl disulfide as a chemical probe. Dimethyl disulfide is a selective reagent with ambident behavior that reacts efficiently with all anions studied and fully capitalizes on the structure/reactivity differences between alkoxides and enolates. Alkoxides behave as classical "hard bases" when allowed to react with dimethyl disulfide, effecting elimination across the C-S bond, whereas enolates, "soft bases", attack at sulfur. Methyl nitrite is also a selective ambident probe reagent but, due to its particularly slow reaction with enolates, is useful only in conjunction with a more reliable probe such as dimethyl disulfide. Methanol-O-d, for a variety of reasons detailed in the paper, is unsuitable as a chemical probe reagent for the unequivocal discernment between alkoxides and enolates.
Gas-Phase Reactions of Fe(1-) and Co(1-) with Simple Thiols, Sulfides, and Disulfides by Fourier Transform Mass Spectrometry
Sallans, L.,Lane, K. R.,Freiser, B. S.
, p. 865 - 873 (2007/10/02)
Fe(1-) and Co(1-) are found to react with simple thiols, sulfides, and disulfides.The primary reaction products formed from these metal anions, M(1-), and thiols include MS(1-), MSH(1-), and MSH2(1-) and suggest a mechanism involving initial insertion of the metal into the weak C-S bond.Similarly, C-S insertion is the main mode of attack in the reactions with the sulfides and disulfides, in analogy to what is observed for the reaction of metal cations.Collision-induced dissociation is used to support the proposed structures for the primary products, H-Fe(1-)-SH andFe(1-)-SH.Some of the thermochemical data derived from this study include D0(M(1-)-S)>103 kcal/mol and D0(M(1-)-SH)=83 +/- 9 kcal/mol.Finally, a brief survey of the reactivity of V(1-), Cr(1-), and Mo(1-) with selected organosulfur compounds is also reported.
