Characterization of Redox States of Ru(OH2)(Q)(tpy)2+ (Q=3,5-di-tert-butyl-1,2-benzoquinone, tpy=2,2′:6′,2-terpyridine) and Related Species through Experimental and Theoretical Studies

The redox states of Ru(OH2)(Q) (tpy)(2+) (Q = 3,5-di-tert-butyl-1,2-benzoquinone, tpy = 2,2':6',2 ''-terpyridine) are investigated through experimental and theoretical UV-vis spectra and Pourbaix diagrams. The electrochemical properties are reported for the species resulting from deprotonation and redox processes in aqueous solution. The formal oxidation states of the redox couples in the various intermediate complexes are systematically assigned using electronic structure theory. The controversy over the electronic assignment of ferromagnetic vs. antiferromagnetic coupling is investigated through comparison of ab initio methods and the broken-symmetry density functional theory (DFT) approach. The various pK(a) values and reduction potentials, including the consideration of proton-coupled electron-transfer (PCET) processes, are calculated, and the theoretical version of the Pourbaix diagram is constructed in order to elucidate and assign several previously ambiguous regions in the experimental diagram,