Electrochemical triggered O-atom transfer reaction in nitrocarbonyl rhenium(I) complexes: An IR spectroelectrochemical investigation

In previous work we proposed that polypyridylrhenium(I)tricarbonyl complexes coordinated to ion nitrite through its N-atom in CH2Cl2 solution could give nitrosyl complexes by electrochemical oxidation. In this work, we report for the first time by IR-spectroelectrochemical measurements that when [ReI(L)(CO)3(NO2)] oxidized to [ReI(L)(CO)3(NO2)]+ with L = 2,2′-bipyridine (bpy) and 4,4′-dimethyl-2,2′-bipyridine (dmb), an O-atom transfer reaction occurs triggered by electrochemical oxidation, leading to a complex with a Re(CO)2(NO) structure and releasing CO2 by an intramolecular mechanism. Additionally, the Re-based oxidation and bipyridyl-based reduction of the nitro-complexes were investigated. The experimental results are in agreement with computational analysis calculated by DFT methods.

Graphical abstractIn [ReI(bpy)(CO)3(NO2)]+ and [ReI(dmb)(CO)3(NO2)]+ (with bpy = 2,2′-bipyridine and dmb = 4,4′-dimethyl-2,2′-bipyridine) an O-atom transfer reaction occurs triggered by electrochemical oxidation leading a Re(CO)2(NO) structure and releasing CO2 by an intramolecular mechanism. The experimental results are in agreement with computational analysis calculated by DFT methods.Figure optionsDownload full-size imageDownload as PowerPoint slide