Cymantrenylmethylidyne, C-c5h4mn(co)3, As a Bridging Ligand for Polymetallic Assembly

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 S[double bond, length half m-dash]CHC5H4 ligand.