Reactions of methyllithium with CO and CNMe: Theoretical study

Hexameric methyllithium was allowed to react with carbon monoxide (or isonitrile) to form a main group metal carbonyl in the first reaction step. The species rearranges to a lithium acetyl via formal insertion of CO into the lithium carbon bond. In a further step, it is seen that a substituted ethane is formed, probably through the formation of an oxycarbene intermediate. The results of density functional theory (DFT) calculations at the B3LYP/6‐31G** level are compared with spectroscopic results, which show the existence of lithium carbonyl and acetyl species (as well as their isonitrile counterparts) at low temperature. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006