The cocondensation reaction of lithium atoms and anisole: an experimental and theoretical study of the reaction pathway

The cocondensation reaction of lithium atoms and pure anisole leads to an ortho CH activation and the formation of lithium hydride. This simple two-component system allows the investigation of the reaction mechanism with included donor molecules. Therefore two anisole and one dilithium molecule, which was identified in an earlier spectroscopic study, were considered for the reaction pathway calculations. Firstly, two intermediates can be found along the reaction pathway, which show the reaction before and after the critical CH activation step. Secondly, a low-lying transition state can be identified, which allows the carbon hydrogen bond to be broken with an activation energy of less than 20 kcal/mol instead of more than 100 kcal/mol, if a free radical mechanism is employed. All calculations were performed at the B3LYP/6-31G** level of theory.