Proton-coupled electron transfer from tyrosine: A strong rate dependence on intramolecular proton transfer distance

Ming Tian Zhang; Tania Irebo; Olof Johansson; Leif Hammarström

doi:10.1021/ja203483j

Proton-coupled electron transfer from tyrosine: A strong rate dependence on intramolecular proton transfer distance

Ming Tian Zhang, Tania Irebo, Olof Johansson, Leif Hammarström

Uppsala University

Research output: Contribution to journal › Article › peer-review

91 Citations (Scopus)

Abstract

Proton-coupled electron transfer (PCET) was examined in a series of biomimetic, covalently linked Ru ^II(bpy) ₃-tyrosine complexes where the phenolic proton was H-bonded to an internal base (a benzimidazyl or pyridyl group). Photooxidation in laser flash/quench experiments generated the Ru ^III species, which triggered long-range electron transfer from the tyrosine group concerted with short-range proton transfer to the base. The results give an experimental demonstration of the strong dependence of the rate constant and kinetic isotope effect for this intramolecular PCET reaction on the effective proton transfer distance, as reflected by the experimentally determined proton donor-acceptor distance.

Original language	English
Pages (from-to)	13224-13227
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	34
DOIs	https://doi.org/10.1021/ja203483j
Publication status	Published - Aug 31 2011

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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abstract = "Proton-coupled electron transfer (PCET) was examined in a series of biomimetic, covalently linked Ru II(bpy) 3-tyrosine complexes where the phenolic proton was H-bonded to an internal base (a benzimidazyl or pyridyl group). Photooxidation in laser flash/quench experiments generated the Ru III species, which triggered long-range electron transfer from the tyrosine group concerted with short-range proton transfer to the base. The results give an experimental demonstration of the strong dependence of the rate constant and kinetic isotope effect for this intramolecular PCET reaction on the effective proton transfer distance, as reflected by the experimentally determined proton donor-acceptor distance.",

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T2 - A strong rate dependence on intramolecular proton transfer distance

AU - Zhang, Ming Tian

AU - Irebo, Tania

AU - Johansson, Olof

AU - Hammarström, Leif

PY - 2011/8/31

Y1 - 2011/8/31

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AB - Proton-coupled electron transfer (PCET) was examined in a series of biomimetic, covalently linked Ru II(bpy) 3-tyrosine complexes where the phenolic proton was H-bonded to an internal base (a benzimidazyl or pyridyl group). Photooxidation in laser flash/quench experiments generated the Ru III species, which triggered long-range electron transfer from the tyrosine group concerted with short-range proton transfer to the base. The results give an experimental demonstration of the strong dependence of the rate constant and kinetic isotope effect for this intramolecular PCET reaction on the effective proton transfer distance, as reflected by the experimentally determined proton donor-acceptor distance.

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Proton-coupled electron transfer from tyrosine: A strong rate dependence on intramolecular proton transfer distance

Abstract

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