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Proton-Coupled Electron Transfer of Ruthenium(III)−Pterin Complexes: A Mechanistic Insight

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Department of Material and Life Science, Graduate School of Engineering, Osaka University, and SORST (JST), 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan, and Department of Chemistry, Campus Box 351700, University of Washington, Seattle, Washington 98195-1700
[email protected]; [email protected]; [email protected]
†Osaka University.
‡Present address: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tennou-dai, Tsukuba, Ibaraki 305-8571, Japan.
§University of Washington.
Cite this: J. Am. Chem. Soc. 2009, 131, 32, 11615–11624
Publication Date (Web):July 28, 2009
https://doi.org/10.1021/ja904386r
Copyright © 2009 American Chemical Society
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Abstract

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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 pKa and bond dissociation energy (BDE) of multistep PCET processes in acetonitrile (MeCN) were determined for ruthenium−pterin complexes, [RuII(Hdmp)(TPA)](ClO4)2 (1), [RuII(Hdmdmp)(TPA)](ClO4)2 (2), [RuII(dmp−)(TPA)]ClO4 (3), and [RuII(dmdmp−)(TPA)]ClO4 (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, [RuIII(dmp−)(TPA)]2+, was determined to be 89 kcal mol−1, which was large enough to achieve hydrogen atom transfer (HAT) from phenol derivatives. In the HAT reactions from phenol derivatives to [RuIII(dmp−)(TPA)]2+, the second-order rate constants (k) were determined to exhibit a linear relationship with BDE values of phenol derivatives with a slope (−0.4), suggesting that this HAT is simultaneous proton and electron transfer. As for HAT reaction from 2,4,6-tri-tert-buthylphenol (TBP; BDE = 79.15 kcal mol−1) to [RuIII(dmp−)(TPA)]2+, the activation parameters were determined to be ΔH⧧ = 1.6 ± 0.2 kcal mol−1 and ΔS⧧ = −36 ± 2 cal K−1 mol−1. This small activation enthalpy suggests a hydrogen-bonded adduct formation prior to HAT. Actually, in the reaction of 4-nitrophenol with [RuIII(dmp−)(TPA)]2+, the second-order rate constants exhibited saturation behavior at higher concentrations of the substrate, and low-temperature ESI-MS allowed us to detect the hydrogen-bonding adduct. This also lends credence to an associative mechanism of the HAT involving intermolecular hydrogen bonding between the deprotonated dmp ligand and the phenolic O−H to facilitate the reaction. In particular, a two-point hydrogen bonding between the complex and the substrate involving the 2-amino group of the deprotonated pterin ligand effectively facilitates the HAT reaction from the substrate to the Ru(III)−pterin complex.

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UV−vis spectra in the spectroscopic titrations to determine the pKa values, the ESR spectrum of 2,4,6-tri-tert-butyl phenoxyl radical obtained by the hydrogen atom transfer reaction from 2,4,6-tri-tert-butyl phenol to [RuIII(dmp−)(TPA)]2+, and the mass spectrum of the reaction product of 4-nitrophenol with [RuIII(dmp−)(TPA)]2+. This material is available free of charge via the Internet at http://pubs.acs.org.

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