Amines from dinitrogen complexes

Berkovich EG, Lenenko VS, Vyshinskaya LI, VasU eva GA, Shur VB, Vol pin ME. Formation of aromatic amines from dinitrogen complexes [CpaTiArJaNa (Ar=C4H5, m-CH3C5H4). J Organomet Chem. 1997 535 169-173. 

One other system shows potential for the production of ammonia and amines from dinitrogen. It was shown several years ago (155) that [(T 5-C5H5)2TiPh2] decomposes thermally via a benzyne intermediate formulated as 42. Such species fix nitrogen. The benzyne complex generated by thermal decomposition as above, or from the reaction of 43 with dinitrogen to form a species formulated as 44. A diphenylacety-... 

Rudienium(Ill) complexes were observed to be sensitive to base hydrolysis as early as 1964. However the difficulties associated with the preparation of suitable complexes and the other attractions of Ru(III) amine chemistry (photochemistry, redox reactions, dinitrogen complexes etc.) tended to divert attention from any systematic study of the base hydrolysis reactions. The most important features that have emerged from the work carried out. Table 3.10, is that substitution invariably takes place with complete retention of configuration and the presence of an amine group tram to the leaving group generates... 

The l-alkyl-3-aryltriazenes (7.15 see Scheme 7-3) are easily obtained from aromatic diazonium salts and alkylamines. They exist in a tautomeric equilibrium (see Zollinger, 1994, Sect. 13.4) and, under acid catalysis, they dissociate into both possible combinations of amine and diazonium ion. The aliphatic amine and aromatic diazonium ion will, however, react further with each other, whereas in the combination alkanediazonium ion -h aromatic amine the diazonium ion will decompose rapidly into the carbocation and dinitrogen. This system has been used little for mechanistic or preparative deamination studies, obviously because a very complex product pattern is inherent in it. The carbocation may react with the aromatic and the aliphatic amine at the amino group. A modified method was described by Southam and Whiting (1982) using anhydrous acetonitrile as medium at —10 to -5°C. ... 

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