Well-Defined Heterometallic and Unsymmetric M2O2 Complexes Arising from Binding and Activation of O2

Well-Defined Heterometallic and Unsymmetric M2O2 Complexes Arising from Binding and Activation of O2:

AbstractOxygen binding and activation reactions at dimetal sites constitute chemical processes of fundamental interest, because of the implication of these reactions in biology, chemical synthesis, and catalysis. This account collects and discusses studies of O₂ binding and/or activation by inequivalent dimetal sites, and it specially focuses on systems in which O₂-bound reaction intermediates have been experimentally characterized. Homometallic unsymmetric systems and heterometallic complexes are reviewed, and their chemistry in oxidative transformations is described. Introduction of asymmetry into M₂O₂ cores poses important challenges to their preparation, and strategies developed to address this problem are discussed. Distinct spectroscopic and chemical properties emerge from these unsymmetric systems.

Oxygen binding and activation at unsymmetric and heterometallic complexes by well-defined MO₂M′ species is reviewed. Studies described so far have provided evidence for a rich chemistry. Novel spectroscopic properties, electronic structures and reactivities are emerging, and they suggest a myriad of fresh avenues still to be explored.