Reaction of •NO thiolate and thiol complexes: Elimination of PhSNO from W(phen)(CO)2(SPh)2, CO from W(phen)(CO)2((-S)2Arene), and HNO from W(phen)(CO)3(RSH)

Kenneth B. Capps, Andreas Bauer, Khalil A. Abboud, Carl D. Hoff

Research output: Contribution to journalArticle

10 Scopus citations

Abstract

Reaction of •NO with W(phen)(CO)2(SPh)2 (phen = 1,10-phenanthroline) results in clean conversion to W(phen)-(CO)2(NO)(SPh). Reduction of the W(II) bisthiolates to the W(0) nitrosyl thiolate occurs with simultaneous reductive elimination of PhS-NO, which is unstable but could be detected spectroscopically. Reaction of W(phen)(CO)2-(1,2-S2-Arene), however, does not result in reductive elimination of either free or bound nitrosothiol. Carbon monoxide is displaced, forming W(phen)(NO)2(1,2-S2-Arene) (1,2-S2-Arene = 1,2-benzene dithiolate or toluene-3,4-dithiolate). Complexes of butanethiol and thiophenol W(phen)(CO)3(RSH) react with excess •NO to form nitrosyl thiolate complexes W(phen)(CO)2(NO)(SR). These reactions also produce N2O and HNO2, which are attributed to decomposition of initially formed HNO. These observations indicate that •NO may be capable of direct attack on complexed thiols. Crystal structures of W(phen)(CO)2(NO)(SPh) and W(phen)(NO)2(toluene-3,4-dithiolate) are reported.

Original languageEnglish (US)
Pages (from-to)6212-6217
Number of pages6
JournalInorganic Chemistry
Volume38
Issue number26
StatePublished - Dec 1 1999

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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