Amine nitrosation via NO reduction of the polyamine copper(II) complex Cu(DAC)(2+)

作者：Khin Chosu; Lim Mark D; Tsuge Kiyoshi; Iretskii Alexei; Wu Guang; Ford Peter C^*

来源：Inorganic Chemistry, 2007, 46(22): 9323-9331.

DOI：10.1021/ic7015929

The reaction of the fluorescent macrocyclic ligand 1, 8-bis (anth racen-9-yl m ethyl)- 1 4,8,11 -tetraazacyclotetradecane with copper(II) salts leads to formation of the Cu(DAC)(2+) cation (1), which is not luminescent. However, when aqueous methanol solutions of I are allowed to react with NO, fluorescence again develops, owing to the formation of the strongly luminescent N-nitrosated ligand DAC-NO (11), which is released from the copper center. This reaction is relatively slow in neutral media, and kinetics studies show it to be first order in the concentrations of NO and base. In these contexts, it is proposed that the amine nitrosation occurs via NO attack at a coordinated amine that has been deprotonated and that this step occurs with concomitant reduction of the Cu(II) to Cu(I). DFT computations at the BP/LACVP* level support these mechanistic arguments. It is further proposed that such nitrosation of electronrich ligands coordinated to redox-active metal centers is a mechanistic pathway that may find greater generality in the biochemical formation of nitrosothiols and nitrosoamines.

• 出版日期2007-10-29