Manganese(I) complexes with (tricyclohexylphosphonio)dithiocarboxylate as chelate and unidentate ligand. X-Ray crystal structure of fac-[Mn(CO)3{S2CP(C6H11)3}2]ClO4·H2O

Abstract

[Mn(CO)₅Br] reacts with S₂CP(C₆H₁₁)₃(C₆H₁₁= cyclohexyl) in refluxing CS₂ to give fac-[Mn(CO)₃{S₂CP(C₆H₁₁)₃}Br](1) which can be also obtained by refluxing cis-[Mn(CO)₄{P(C₆H₁₁)₃}Br] in CS₂. Halide abstraction from (1) with AgClO₄, and subsequent treatment with neutral ligands L affords fac-[Mn(CO)₃L{S₂CP(C₆H₁₁)₃}]ClO₄ with L = CO, P(OMe)₃, P(C₆H₁₁)₃, S₂CP(C₆H₁₁)₃. In the case of L = S₂CP(C₆H₁₁)₃ an X-ray structure determination shows that the resulting compound fac-[Mn(CO)₃{S₂CP(C₆H₁₁)₃}₂]ClO₄ contains one S₂CP(C₆H₁₁)₃ acting as a chelate (SS′) ligand and another acting in a unidentate σ-(S) fashion. Compounds [Mn(CO)₅{S₂CP(C₆H₁₁)₃}]ClO₄ and fac-[Mn(CO)₃(L–L){S₂CP(C₆H₁₁)₃}]ClO₄(L–L = Ph₂PCH₂PPh₂ or 2,2′-bipyridyl) containing unidentate S₂CP(C₆H₁₁)₃ ligands can be obtained by displacement of OClO₃^– from perchlorate complexes.