Electrochemical triggered O-atom transfer reaction in nitrocarbonyl

DOMINGUEZ, SOFÍA E; FAGALDE, FLORENCIA

POLYHEDRON

PERGAMON-ELSEVIER SCIENCE LTD

Lugar: Amsterdam; Año: 2015 vol. 100 p. 114 - 120

0277-5387

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