Bi- and Tetranuclear Tricarbido Complexes: μ,σ:σ‘ and μ,σ:σ‘:π⊥ Coordination of Bridging C3 Ligands

Fluoride-mediated desilylation of the propargylidyne [W(⋮CC⋮CSiMe 3 )(CO) 2 {HB(pz) 3 }] ( 1; pz = pyrazol-1-yl) in the presence of [RhCl(CO)(PPh 3 ) 2 ] provides the bimetallic complex [Rh(C⋮CC⋮W(CO) 2 {HB(pz) 3 })(CO)(PPh 3 ) 2 ] ( 2b ), which reacts with iodine to give [Rh(C⋮CC⋮W(CO) 2 {HB(pz) 3 })I 2 (CO)(PPh 3 ) 2 ] ( 3 ) and with [Fe 2 (CO) 9 ] to provide [RhFe 2 (μ-C 3 W(CO) 2 {HB(pz) 3 })(CO) 10 (PPh 3 )] ( 4 ), a rare example of a tricarbido ligand incorporated within a cluster framework.