Superoxide to Peroxide Interconversion in Ni-TMC Complexes: The Significance of Structure and Spin States.

Abstract

A deeper comprehension of the characteristics of metal-superoxide and metal-peroxide chemical species is imperative, considering their pivotal functions in oxygen transport, enzymatic activation, and catalytic oxygenations. O2 activation is mediated by the interconversion of superoxide and peroxide species. Even though there are multiple studies on metal-superoxide and -peroxide intermediates, robust examples of their interconversion processes are scarce synthetically. For example, Ni-superoxide/peroxide complexes have been characterized with N-Tetramethylated Cyclam (TMC) ligands with different ring sizes, i.e., Nickel(II)-superoxide complex is characterized with 14-TMC while Nickel(III)-peroxide complex with 12-TMC. Later, both complexes were obtained with 13-TMC ligand by employing different bases; interestingly, no evidence of interconversion between them was identified. What are the factors influencing these processes and why is this preference? We attempt a computational analysis of this issue and provide arguments based on our conclusions. 2-dimensional potential energy scan is performed on the 12-TMC, 13-TMC, and 14-TMC systems to identify the reaction path connecting superoxide and peroxide species. Analyses indicate that structure and spin states play a significant role in determining the probability of interconversion. The superoxide-peroxide interconversion process appears to be bound by their propensity for distinct structural features and spin states.