Unusual Water Oxidation Mechanism via a Redox-Active Copper Polypyridyl Complex
Daan den Boer, Andrey I. Konovalov, Maxime A. Siegler, Dennis G. H. Hetterscheid
Abstract
High Resolution Image Download MS PowerPoint Slide To improve Cu-based water oxidation (WO) catalysts, a proper mechanistic understanding of these systems is required. In contrast to other metals, high-oxidation-state metal–oxo species are unlikely intermediates in Cu-catalyzed WO because π donation from the oxo ligand to the Cu center is difficult due to the high number of d electrons of Cu II and Cu III . As a consequence, an alternative WO mechanism must take place instead of the typical water nucleophilic attack and the inter- or intramolecular radical–oxo coupling pathways, which were previously proposed for Ru-based catalysts. [Cu II (H L )(OTf) 2 ] [H L = Hbbpya = N, N -bis(2,2′-bipyrid-6-yl)amine)] was investigated as a WO catalyst bearing the redox-active H L ligand. The Cu catalyst was found to be active as a WO catalyst at pH 11.5, at which the deprotonated complex [Cu II ( L – )(H 2 O)] + is the predominant species in solution. The overall WO mechanism was found to be initiated by two proton-coupled electron-transfer steps. Kinetically, a first-order dependence in the catalyst, a zeroth-order dependence in the phosphate buffer, a kinetic isotope effect of 1.0, a Δ H ⧧ value of 4.49 kcal·mol –1, a Δ S ⧧ value of −42.6 cal·mol –1 ·K –1, and a Δ G ⧧ value of 17.2 kcal·mol –1 were found. A computational study supported the formation of a Cu–oxyl intermediate, [Cu II ( L • )(O • )(H 2 O)] + . From this intermediate onward, formation of the O–O bond proceeds via a single-electron transfer from an approaching hydroxide ion to the ligand. Throughout the mechanism, the Cu II center is proposed to be redox-inactive.