Unusual Reaction Pathways in the Photolysis of Diazido(phosphane)nickel(II) Complexes: Nitrenes As Intermediates in the Formation of Nickel(o) Complexes

摘要

The photochemical specificity of azide ligands is due to their redox behavior: depending on the central ion nitrido complexes, azidyl radicals, or nitrene intermediates form. Whereas photochemical redox reactions with participation of the central ionare well described, only with azido complexes of iridium(III), rhodium(III), and diazidonickel(II) complexes with azamacrocycles as ligands have photochemical nitrene reaction pathways been observed, and then indirectly by secondary hydrazine formation.We were able to show that the primary photoreaction due to charge transfer (CT) excitation of nickel(II) complexes of the constitution [Ni("P_2")(N_3)_2] (P_2: mono- and diphosphane ligands; 1-4) leads to the generation of nitrenes as intermediates.