Transformations of molecular nitrogen into aromatic amines under the action of titanium compounds

Abstract The paper describes remarkable reactions of the direct synthesis of aromatic amines from molecular nitrogen. Two types of systems capable of inducing such reactions are considered in detail. The first type involves systems based on titanium compounds (Cp 2 TiCl 2 , Cp 2 TiPh 2 , CpTiCl 3 , TiCl 4 , Ti(OBu) 4 ) and excess aryllithium reagents (PhLi, p-, m- and o -MeC 6 H 4 Li, α-C 10 H 8 Li, o PhC 6 H 4 Li) in ether. The second type is obtained by treating diaryltitanocenes Cp 2 TiAr 2 (Ar = Ph, p- and m -MeC 6 H 4 ) with metals of groups I and II (Li, Na, Mg) in ethereal media. In both cases the interaction with dinitrogen proceeds at room temperature and results in the formation of aromatic amines and ammonia after hydrolysis. The highest activity in amine production is displayed by the systems Cp 2 TiCl 2 + PhLi in ether and Cp 2 TiPh 2 + Li in THF. The mechanism of the reactions found is discussed.