The Enthalpy of Insertion of Sulfur into the Metal-Hydrogen Bond. Synthetic, Structural, and Calorimetric Study of the Complexes HS-M(CO)(3)C(5)R(5) [M = Cr, Mo, W; R = H, Me].

Synthetic and calorimetric studies of the sulfhydryl complexes HS-M(CO)(3)C(5)R(5) (M = Cr, R = Me; M = Mo, W, R = H, Me) are reported. The Mo and W complexes can be obtained in high yield by reaction of the hydrido complexes H-M(CO)(3)C(5)R(5) with Ph(3)Sb=S, which readily undergoes single S atom transfer to the metal-hydrogen bond yielding the metal-sulfhydryl complex. Direct reaction between the metal hydrides and a limited amount of sulfur also yields the sulfhydryl complexes as the dominant organometallic product.