| Abstract: | Oxidative addition of diphenyl disulfide to the coordinatively unsaturated Mn(CO)5]? led to the formation of low-spin, six-coordinate cis-Mn(CO)4(SPh)2]?. The complex cis-PPN]Mn(CO)4(SPh)2] crystallized in monoclinic space group P21/c with a = 9.965(2) Å, b = 24.604(5) Å, c = 19.291(4) Å, β = 100.05(2)°, V = 4657(2)Å3, and Z = 4; final R = 0.036 and Rw = 0.039. Thermal transformation of cis-Mn(CO)4(SPh)2]? to (CO)3Mn(μ-SPh)3Mn(CO)3]? was completed overnight in THF at room temperature. Additionally, reaction of Mn(CO)5]? and PhSH in 1:2 mole ratio also led to cis-PPN](Mn(CO)4(SPh)2]. Presumably, oxidative addition of PhSH to Mn(CO)4]? was followed by a Lewis acid-base reaction to form cis-Mn(CO)4(SPh)2]? with evolution of H2. |
