A DFT STUDY ON CO INSERTION AND C–C REDUCTIVE ELIMINATION INVOLVED IN THE CARBONYLATION OF METALLACYCLIC ZIRCONACENES

Abstract

CO insertion and C–C reductive elimination involved in the carbonylation of the metallacyclic zirconocene complex, 1,1-bis(η5-cyclopentadienyl)-1-zirconaindan (R), have been theoretically studied with the aid of DFT calculations at the B3LYP level. It is found that the C(sp3)-C(sp2) reductive elimination is preferred over C(sp2)-C(sp2) , and importantly, this preference for C–C reductive elimination directs the CO insertion into the Zr-C(sp2) bond rather than the Zr-C(sp3) bond, even though the CO insertion into the former bond is kinectically less favorable than into the latter bond, a result related to that the CO insertion is found to be reversible.