CHEMISTRY OF VINYLIDENE COMPLEXES. I. CONVERSION OF VINYLIDENE MANGANESE COMPLEXES INTO ?-OLEFINIC COMPLEXES BY ACTION OF PHOSPHITES. CRYSTAL AND MOLECULAR STRUCTURE OF η5-CYCLOPENTADIENYLDICARBONYL-(η2-trans-1-DIETHYLPHOSPHONATO-2-PHENYLETHYLENE)MANGANESE,...

Article abstract of DOI:10.1016/S0022-328X(00)98631-5

The novel reaction of the manganese vinylidene complex Cp(CO)2Mn=C=CHPh with P(OR)3 (R=Et or Ph) affords the olefinic complexes of the type Cp(CO)2Mn under mild conditions.This conversion may be interpreted as an unusual variant of the Arbuzov reaction occurring in the coordination sphere of a transition metal atom which is accompanied by an n-? rearrangement of the organic ligand.The X-ray study of the complex Cp(CO)2Mn shows that the phosphonatoethylene ligand is coordinated by the manganese atom as an η²-olefin and that the substituents at the C=C bond are in trans positions.IR and 1H NMR spectra of the complexes are discussed.A probable mechanistic scheme for the reaction is proposed.