Concerted proton-electron transfer to dioxygen in water

Ophir Snir, Yifeng Wang, Mark Tuckerman, Yurii V. Geletii, Ira A. Weinstock

Research output: Contribution to journalArticle

Abstract

Concerted proton-electron transfer (CPET) is documented for the homogeneous reduction of O2 to HO2· in water by the one-electron-reduced heteropolytungstate anion, α-PW12O 404- (11e). At 0.01-0.3 M H+, O 2 reduction occurs via outer-sphere electron transfer followed by proton transfer (ETPT, with rate constant kET). Between 0.30 and 1.9 M H+, rates increase linearly with [H+] due to a parallel CPET pathway in which H+ is now a reactant: (1/2)kobs = kET + kCPET[H+] (kET = 1.2 M -1 s-1; kCPET = 0.8 M-2 s -1). Control experiments rule out preassociation between H + and 11e. Analysis of plausible rate expressions shows that the first-order dependence on [H+] is uniquely consistent with multisite CPET, and a deuterium kinetic isotope effect of 1.7 is observed. Reductions of O2 by α-SiW12O40 5- confirm theoretical predictions that CPET decreases in significance as ET becomes less endergonic. Marcus analysis, including the temperature dependence of ΔG°, gives reorganization energies, λET = 41.5 kcal mol-1 and λCPET = 52.4 kcal mol-1. At 1.5 M H+, ∼75% of the (1 1e,O2) encounter pairs form within 6 Å of H + ions. This value (6 ± 1 Å) is the "reaction distance" for proton diffusion and probably close to that for CPET. Even so, the 70-200 ps lifetimes of the (11e,O2) pairs provide additional time for H+ to diffuse closer to O2. CPET is first-order in [H+] because ke for "cage escape" from (11e,O2) pairs is much larger than kCPET, such that the rate expression for CPET becomes -(1/2)d[11e]/dt = (kd/ke)kCPET[11e][O 2][H+], where kd is the rate constant for (11e,O2) pair formation. Overall, the findings suggest that the emergence of CPET, with hydronium ion as the proton donor, may prove a general feature of sufficiently endergonic reductions of dioxygen by otherwise "outer-sphere" complexes (or electrode reactions) at sufficiently low pH values in water.

Original languageEnglish (US)
Pages (from-to)11678-11691
Number of pages14
JournalJournal of the American Chemical Society
Volume132
Issue number33
DOIs
StatePublished - Aug 25 2010

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Protons
Electrons
Oxygen
Water
Hydrogen
Rate constants
Proton transfer
Deuterium
Ions
Isotopes
Anions
Negative ions
Electrodes
Kinetics
Temperature

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Concerted proton-electron transfer to dioxygen in water. / Snir, Ophir; Wang, Yifeng; Tuckerman, Mark; Geletii, Yurii V.; Weinstock, Ira A.

In: Journal of the American Chemical Society, Vol. 132, No. 33, 25.08.2010, p. 11678-11691.

Research output: Contribution to journalArticle

Snir, Ophir ; Wang, Yifeng ; Tuckerman, Mark ; Geletii, Yurii V. ; Weinstock, Ira A. / Concerted proton-electron transfer to dioxygen in water. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 33. pp. 11678-11691.
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abstract = "Concerted proton-electron transfer (CPET) is documented for the homogeneous reduction of O2 to HO2· in water by the one-electron-reduced heteropolytungstate anion, α-PW12O 404- (11e). At 0.01-0.3 M H+, O 2 reduction occurs via outer-sphere electron transfer followed by proton transfer (ETPT, with rate constant kET). Between 0.30 and 1.9 M H+, rates increase linearly with [H+] due to a parallel CPET pathway in which H+ is now a reactant: (1/2)kobs = kET + kCPET[H+] (kET = 1.2 M -1 s-1; kCPET = 0.8 M-2 s -1). Control experiments rule out preassociation between H + and 11e. Analysis of plausible rate expressions shows that the first-order dependence on [H+] is uniquely consistent with multisite CPET, and a deuterium kinetic isotope effect of 1.7 is observed. Reductions of O2 by α-SiW12O40 5- confirm theoretical predictions that CPET decreases in significance as ET becomes less endergonic. Marcus analysis, including the temperature dependence of ΔG°, gives reorganization energies, λET = 41.5 kcal mol-1 and λCPET = 52.4 kcal mol-1. At 1.5 M H+, ∼75{\%} of the (1 1e,O2) encounter pairs form within 6 {\AA} of H + ions. This value (6 ± 1 {\AA}) is the {"}reaction distance{"} for proton diffusion and probably close to that for CPET. Even so, the 70-200 ps lifetimes of the (11e,O2) pairs provide additional time for H+ to diffuse closer to O2. CPET is first-order in [H+] because ke for {"}cage escape{"} from (11e,O2) pairs is much larger than kCPET, such that the rate expression for CPET becomes -(1/2)d[11e]/dt = (kd/ke)kCPET[11e][O 2][H+], where kd is the rate constant for (11e,O2) pair formation. Overall, the findings suggest that the emergence of CPET, with hydronium ion as the proton donor, may prove a general feature of sufficiently endergonic reductions of dioxygen by otherwise {"}outer-sphere{"} complexes (or electrode reactions) at sufficiently low pH values in water.",
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AU - Snir, Ophir

AU - Wang, Yifeng

AU - Tuckerman, Mark

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AU - Weinstock, Ira A.

PY - 2010/8/25

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N2 - Concerted proton-electron transfer (CPET) is documented for the homogeneous reduction of O2 to HO2· in water by the one-electron-reduced heteropolytungstate anion, α-PW12O 404- (11e). At 0.01-0.3 M H+, O 2 reduction occurs via outer-sphere electron transfer followed by proton transfer (ETPT, with rate constant kET). Between 0.30 and 1.9 M H+, rates increase linearly with [H+] due to a parallel CPET pathway in which H+ is now a reactant: (1/2)kobs = kET + kCPET[H+] (kET = 1.2 M -1 s-1; kCPET = 0.8 M-2 s -1). Control experiments rule out preassociation between H + and 11e. Analysis of plausible rate expressions shows that the first-order dependence on [H+] is uniquely consistent with multisite CPET, and a deuterium kinetic isotope effect of 1.7 is observed. Reductions of O2 by α-SiW12O40 5- confirm theoretical predictions that CPET decreases in significance as ET becomes less endergonic. Marcus analysis, including the temperature dependence of ΔG°, gives reorganization energies, λET = 41.5 kcal mol-1 and λCPET = 52.4 kcal mol-1. At 1.5 M H+, ∼75% of the (1 1e,O2) encounter pairs form within 6 Å of H + ions. This value (6 ± 1 Å) is the "reaction distance" for proton diffusion and probably close to that for CPET. Even so, the 70-200 ps lifetimes of the (11e,O2) pairs provide additional time for H+ to diffuse closer to O2. CPET is first-order in [H+] because ke for "cage escape" from (11e,O2) pairs is much larger than kCPET, such that the rate expression for CPET becomes -(1/2)d[11e]/dt = (kd/ke)kCPET[11e][O 2][H+], where kd is the rate constant for (11e,O2) pair formation. Overall, the findings suggest that the emergence of CPET, with hydronium ion as the proton donor, may prove a general feature of sufficiently endergonic reductions of dioxygen by otherwise "outer-sphere" complexes (or electrode reactions) at sufficiently low pH values in water.

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