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Proton-coupled electron transfer of ruthenium(III)-pterin complexes: a mechanistic insight.


ABSTRACT: Ruthenium(II) complexes having pterins of redox-active heteroaromatic coenzymes as ligands were demonstrated to perform multistep proton transfer (PT), electron transfer (ET), and proton-coupled electron transfer (PCET) processes. Thermodynamic parameters including pK(a) and bond dissociation energy (BDE) of multistep PCET processes in acetonitrile (MeCN) were determined for ruthenium-pterin complexes, [Ru(II)(Hdmp)(TPA)](ClO(4))(2) (1), [Ru(II)(Hdmdmp)(TPA)](ClO(4))(2) (2), [Ru(II)(dmp(-))(TPA)]ClO(4) (3), and [Ru(II)(dmdmp(-))(TPA)]ClO(4) (4) (Hdmp = 6,7-dimethylpterin, Hdmdmp = N,N-dimethyl-6,7-dimethylpterin, TPA = tris(2-pyridylmethyl)amine), all of which had been isolated and characterized before. The BDE difference between 1 and one-electron oxidized species, [Ru(III)(dmp(-))(TPA)](

SUBMITTER: Miyazaki S 

PROVIDER: S-EPMC3201791 | biostudies-literature | 2009 Aug

REPOSITORIES: biostudies-literature