End-on versus side-on coordination of dinitrogen to titanium-benzene complex

Titanium atoms react with dinitrogen and benzene mixtures in solid argon to form the end-on bonded Ti(η6-C6H6)(η1-NN) and Ti(η6-C6H6)(η1-NN)2 complexes, which photochemically rearrange to the side-on bonded Ti(η6-C6H6)(η2-N2) and Ti(η6-C6H6)(η1-NN)(η2-N2) isomers with a more activated N2.