Use of the MnCC system in organometallic and organic synthesis

Abstract The present review summarizes the syntheses, structures, physicochemical properties and reactivity of complexes containing η 1 -, μ-, μ 3 - and μ 4 -vinylidene ligands. Consideration of mononuclear vinylidene complexes is limited to cymantrene derivatives, one of which, viz. Cp(CO) 2 Mn C CHPh ( 1 ), has served as the precursor for syntheses of many organometallic and some organic compounds. The reactions between phosphites P(OR) 3 and complex 1 afford styrylphosphonates PhCH CHP(O)(OR) 2 . All the transformations of complex 1 occur under very mild conditions. Special attention is paid to heterometallic complexes , containing Mn, Fe and the platinum Group metals with bridging vinylidene ligands. The Mn C CHR system is used as a “building block” for a series of dimetal μ-vinylidene complexes including Mn M bonds (M = Mo, W, Mn, Re, Fe, Rh, Pd, Pt, Cu) and trimetallic MnFePt μ 3 -vinylidene clusters. Transmetalation reactions of the MnPd and MnPt complexes have given a series of μ 4 -vinylidene PdFe 3 and PtFe 3 clusters. Transfer of vinylidene from the Mn atom to another metal atom (Re), to the dinuclear (FePt) and cluster (Os 3 , PdFe 3 , PtFe 3 ) systems has been shown. A systematic study of a dependence of structural and spectroscopic parameters of mono-, di-, tri- and tetra-nuclear complexes on the vinylidene coordination mode has been carried out.