Formation of aromatic amines from dinitrogen complexes [Cp2TiAr]2N2 (Ar = C6H5, m-CH3C6H4)

Article abstract of DOI:10.1016/S0022-328X(96)06958-6

It has been shown that the reaction of the dinitrogen complex [Cp₂TiC₆H₅]₂N₂ with a mixture of C₆H₅Li and Li in ether results in the formation of ammonia and aniline after hydrolysis. Under optimum conditions, the yield of aniline is 12 mol% per initial complex and the ammonia yield is 36 mol%. In the absence of lithium neither ammonia nor aniline are formed, while in the absence of phenyllithium only ammonia is produced. The interaction of [Cp₂TiC₆H₅]₂N₂ with p-, m-and o-tolyllithium reagents in the presence of lithium also gives aromatic amines and ammonia after hydrolysis. Similar results have been obtained for the dinitrogen complex [Cp₂Ti(m-CH₃C₆H₄)]₂N₂. The mechanism of the reaction found is discussed.