Selective Catalysis by Complexes Including Ni and Redox-Inactive Alkali Metals (Li, Na, or K) in Oxidation Processes: The Role of Hydrogen Bonds and Supramolecular Structures.

It is known that the presence of redox-inactive metals in the active center of an enzyme has a significant effect on its activity. In this regard and for other reasons, the effect of redox-inactive metals on redox processes, such as electron transfer, oxygen and hydrogen atom transfer, as well as the breaking and formation of O-O bonds in reactions catalyzed by transition metals, has been widely studied. Many questions about the role of redox-inactive metals in the mechanisms of these reactions remain open. In this paper, the mechanism of catalysis by bi- and triple hetero-binuclear heteroligand complexes including Ni and redox-inactive alkali metals ((A) {Ni(acac)∙L} and (B) {Ni(acac)∙L∙PhOH} (L = MSt (M = Li, Na, or K)) in the process of the selective oxidation of ethylbenzene by molecular oxygen into α-phenyl ethyl hydroperoxide is considered. The activity of A and B complexes towards O, ROOH, and RO radicals was studied. Based on kinetic data, we suggest that the high catalytic efficiency of B triple complexes in oxidation processes may be associated with the role of outer-sphere regulatory interactions, with the formation of stable supramolecular structures due to intermolecular H bonds. This assumption was confirmed using the AFM method. Prospects for studying catalysis by complexes ({Ni(acac)∙L} and {Ni(acac)∙L∙PhOH}) that are models of NiARD (Ni-Acyreductone dioxygenase) are discussed.