Long-range proton-coupled electron transfer in phenol–Ru(2,2′-bipyrazine)32+ dyads
نویسندگان
چکیده
منابع مشابه
Proton-coupled electron transfer.
Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several areas where the transfer of an electron and proton is tightly coupled and discuss model systems that can provide an experimental basis for a test of PCET theory. In a PCET reaction, the electron and proton may tran...
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Tyramine β-monooxygenase (TβM) belongs to a family of physiologically important dinuclear copper monooxygenases that function with a solvent-exposed active site. To accomplish each enzymatic turnover, an electron transfer (ET) must occur between two solvent-separated copper centers. In wild-type TβM, this event is too fast to be rate limiting. However, we have recently shown [Osborne, R. L.; et...
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Concerted proton-electron transfer (CPET) reactions in iron carboxy-tetraphenylporphyrin complexes have been investigated using both experimental and theoretical methods. Synthetic heme models abstract H+ and e- from the hydroxylamine TEMPOH or an ascorbate derivative, and the kinetics of the TEMPOH reaction indicate concerted transfer of H+ and e-. Phenylene linker domains vary the electron do...
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Recent investigations have shed much light on the nuclear and electronic factors that control the rates of long-range electron tunneling through molecules in aqueous and organic glasses as well as through bonds in donor-bridge-acceptor complexes. Couplings through covalent and hydrogen bonds are much stronger than those across van der Waals gaps, and these differences in coupling between bonded...
متن کاملKinetics of proton-coupled electron-transfer reactions
The kinetics of proton-coupled electron-transfer (pcet) reactions are reported for Mn4O4(O2PPh2)6, 1, and [Mn4O4(O2PPh2)6] , 1 , with phenothiazine (pzH). Both pcet reactions form 1H, by H transfer to 1 and by hydride transfer to 1 . Surprisingly, the rate constants differ by only 25% despite large differences in the formal charges and driving force. The driving force is proportional to the dif...
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ژورنال
عنوان ژورنال: Physical Chemistry Chemical Physics
سال: 2014
ISSN: 1463-9076,1463-9084
DOI: 10.1039/c3cp55071k