Photochemical reaction of the 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecanenickel (II)-y-diazido-5,7,7,12,14,14-hexamethyl-l,4, 8,11-tetraazacyclotetradecanenickel (II) tetrafluoroborate

摘要

Photolysis of methanolic solutions of (Ni(tet-b)N3)2^2 +, containing ammonia, various olefins and ammonium tetrafluoroborate, results in the formation of hydrazine and possibly aziridine derivatives. The data have been interpreted in terms of the formation of a coordinated nitrene. A nitrene intermediate is also implicated by the kinetic results. Quantum yields were determined at 340 nm. The kinetics of the photochemical reactions have been studied and a mechanism is proposed to explain the primary steps induced by photolysis. Scavenger concentration studies show that the quantum yield of hydrazine increases with increasing concentration of ammonia and decreases with increasing concentration of olefin. The results suggest that the olefin does effectively scavenge the intermediate to form aziride derivatives.