Cymantrenylmethylidyne, C–C5H4Mn(CO)3′ as a bridging ligand for polymetallic assembly

Abstract

The reaction of [Mn(CO)₃(η⁵-C₅H₄Li)] with [M(CO)₆], (CF₃CO)₂O and L₂[M = W, L₂=N,N,N′,N′-tetramethylethylenediamine (tmen); M = Mo, L₂= 2,2′-bipyridyl (bipy)] affords the cymantrenylmethylidyne complexes [MMn(µ-σ:η⁵-CC₅H₄)(CO)₅L₂(O₂CCF₃)]. One manganese-bound carbonyl ligand in the alkylidynetungsten complex is photolabile in tetrahydrofuran leading to [WMn(µ-σ:η⁵-CC₅H₄)(CO)₄(thf)(tmen)(O₂CCF₃)]. Treating the molybdenum complex with NaC₅H₅·MeOC₂H₄OMe or K[HB(pz)₃](pz = pyrazol-1-yl) provides the complexes [MoMn(µ-σ:η⁵-CC₅H₄)(CO)₅L′][L′=η-C₅H₅ or HB(pz)₃]. Reactions of the former with [Ni(cod)₂](cod = cycloocta-1,5-diene) or [Co₂(CO)₈] give the penta- and tetra-metallic compounds [Mo₂Mn₂Ni(µ₃-σ:σ′:η⁵-CC₅H₄)₂(CO)₁₀(η-C₅H₅)₂] and [MoMnCo₂(µ₄-σ:σ′:σ″:η⁵-CC₅H₄)(CO)₁₁(η-C₅H₅)]. Treatment of [WMn(µ-σ:η⁵-CC₅H₄)(CO)₅(tmen)(O₂CCF₃)] with [NH₂Et₂][S₂CNEt₂] provides a complex [WMn(µ-η²:η⁵-SCHC₅H₄)(CO)₄(S₂CNEt₂-S,S′)(η²-SCNEt₂)] bearing the unusual SCHC₅H₄ ligand.