Hydride thiolate derivatives of low valent iron complexes

Vita.The highly electron-rich, bis(phosphite) iron hydride complex [Et4N][HFe(CO)2(P(OPh)3)2] has provided synthetic entry to the simple, mono-functional iron thiolates (ArS)Fe(CO)2(P(OPh)3)2- (Ar = Ph, Tol). Both the metal center, and the sulfur atom of the thiolate ligand provide sites for reactivity with electrophiles such as R+ and H+. Methylation of the anionic thiolate results in the formation of the thioether species (ArSMe)Fe(CO)2(P(OPh)3)2, while protonation results in the formation of the thiolate-hydride complex (ArS)Fe(H) (CO)2(P(OPh)3)2. These complexes have been characterize by nuclear magnetic resonance and infrared spectroscopies. (PhS)Fe(H)(CO)2(P(OPh)3)2 was characterized by single-crystal X-ray diffraction. (PhS)Fe(H)(CO)2(P(OPh)3)2 was protonated to form the novel, cationic thiol-hydride complex (PhSH)Fe(H)(CO)2(P(OPh)3)2+