Dinuclear oxidative addition of N-H and S-H bonds at chromium. Reaction of (*)Cr(CO)(3)(C(5)Me(5)) with [o-(HA)C(6)H(4)S-Cr(CO)(3)(C(5)Me(5))] (A = S, NH) yielding [eta(2)-o-(mu-A)C(6)H(4)S-Cr(C(5)Me(5))](2) and H-Cr(CO)(3)(C(5)Me(5)).

Reaction of the 17-electron radical (*)Cr(CO)(3)Cp* (Cp* = C(5)Me(5)) with 0.5 equiv of 2-aminophenyl disulfide [(o-H(2)NC(6)H(4))(2)S(2)] results in rapid oxidative addition to form the initial product (o-H(2)N)C(6)H(4)S-Cr(CO)(3)Cp*. Addition of a second equivalent of (*)Cr(CO)(3)Cp* to this solution results in the formation of H-Cr(CO)(3)Cp* as well as (1)/(2)[[eta(2)-o-(mu-NH)C(6)H(4)S]CrCp*](2).

Mechanistic Study of the Reaction of (*)Cr(CO)(3)C(5)Me(5) with H(2)S Yielding HCr(CO)(3)C(5)Me(5), HSCr(CO)(3)C(5)Me(5), and C(5)Me(5)(CO)(2)Cr=S=Cr(CO)(2)C(5)Me(5). Kinetic Evidence for Formation of the Substituted Radical Complex (*)Cr(CO)(2)(H(2)S)C(5)Me(5).

Reaction of a large excess of H(2)S with 2 mol of (*)Cr(CO)(3)C(5)Me(5) yields HCr(CO)(3)C(5)Me(5) and HSCr(CO)(3)C(5)Me(5). Kinetic studies of this reaction show two reaction pathways are followed. At pressures of CO above 10-15 atm and temperatures View Article and Find Full Text PDF