Reaction of *NO Thiolate and Thiol Complexes: Elimination of PhSNO from W(phen)(CO)(2)(SPh)(2), CO from W(phen)(CO)(2)((-S)(2)Arene), and HNO from W(phen)(CO)(3)(RSH).
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-S(2)-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-S(2)-Arene) (1,2-S(2)-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 N(2)O and HNO(2), 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.
Capps
Kenneth B.
KB
Department of Chemistry, University of Miami, Coral Gables, Florida 33124, and Department of Chemistry, University of Florida, Gainesville, Florida 32611.
Bauer
Andreas
A
Abboud
Khalil A.
KA
Hoff
Carl D.
CD