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

Wen-Feng Liaw, Chao-Yi Ching, Chen-Kang Lee, Gene-Hsiang LeeShie-Ming Peng
Journal of the Chinese Chemical Society, 卷.43(5), 頁碼.427-431
1996

摘要

Manganese (I)-phenylthiolate derivatives Chemistry (all)
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) 5 ] - was followed by a Lewis acid-base reaction to form cis-[Mn(CO) 4 (SPh) 2 ] - with evolution of H 2 .

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