Oxidative Addition of Diphenyl Disulfide/Thiophenol to [Mn(CO) 5 ] − : Crystal Structure of cis ‐[Mn(CO) 4 (SPh) 2 ] −

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 P2 1 /c with a = 9.965(2) Å, b = 24.604(5) Å, c = 19.291(4) Å, β = 100.05(2)°, V = 4657(2)Å 3 , and Z = 4; final R = 0.036 and R w = 0.039. Thermal transformation of cis ‐[Mn(CO) 4 (SPh) 2 ] − to [(CO) 3 Mn(μ‐SPh) 3 Mn(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 H 2 .