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Gas-phase reactions of Fe sup minus and Co sup minus with simple thiols, sulfides, and disulfides by Fourier transform mass spectrometry

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00185a013· OSTI ID:5119665
; ;  [1]
  1. Purdue Univ., West Lafayette, IN (USA)
Fe{sup {minus}} and Co{sup {minus}} are found to react with simple thiols, sulfides, and disulfides. The primary reaction products formed from these metal anions, M{sup {minus}}, and thiols include MS{sup {minus}}, MSH{sup {minus}}, and MSH{sub 2}{sup {minus}} 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{sup {minus}}-SH and Fe{sup {minus}}-SH. Some of the thermochemical data derived from this study include D{degree}(M{sup {minus}}-S) > 103 kcal/mol and D{degree}(M{sup {minus}}-SH) = 83 {plus minus}9 kcal/mol. Finally, a brief survey of the reactivity of V{sup {minus}}, Cr{sup {minus}}, and Mo{sup {minus}} with selected organosulfur compounds is also reported. 79 refs., 3 figs., 7 tabs.
DOE Contract Number:
FG02-87ER13766
OSTI ID:
5119665
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:3; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English