Electron transfer reactivity of the aqueous iron(IV)–oxo complex. Outer-sphere vs proton-coupled electron transfer

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

doi:10.1021/acs.inorgchem.6b00966

Title: Electron transfer reactivity of the aqueous iron(IV)–oxo complex. Outer-sphere vs proton-coupled electron transfer

Journal Article · Sat Jun 18 00:00:00 EDT 2016 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.6b00966· OSTI ID:1259478

Bataineh, Hajem ^[1]; Pestovsky, Oleg ^[1]; Bakac, Andreja ^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States)

Here, the kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, Fe^IV(H₂O)₅O²⁺ (hereafter Fe^IV_aqO²⁺), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN)₃²⁺ (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS–/ABTS^2–, phenothiazines, Co^II(dmgBF₂)₂, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generated ligand-modified products. Fe^IV_aqO²⁺ oxidizes even Ce(III) (E⁰ in 1 M HClO₄ = 1.7 V) with a rate constant greater than 10⁴ M^–1 s^–1. In 0.10 M aqueous HClO₄ at 25 °C, the reactions of Os(phen)₃²⁺ (k = 2.5 × 10⁵ M^–1 s^–1), IrCl₆^3– (1.6 × 10⁶), ABTS^2– (4.7 × 10⁷), and Fe(cp)(C₅H₄CH₂OH) (6.4 × 10⁷) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen)₃²⁺ and of ferrocenes remained unchanged in the acidity range 0.05 < [H+] < 0.10 M, ruling out prior protonation of Fe^IV_aqO²⁺ and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k₂₂ + E⁰_Fe/0.059) = 17.2 ± 0.8, where k₂₂ and E⁰_Fe are the self-exchange rate constant and reduction potential, respectively, for the Fe^IV_aqO²⁺/Fe^III_aqO⁺ couple. Comparison with literature work suggests k₂₂ < 10^–5 M^–1 s^–1 and thus E⁰(Fe^IV_aqO²⁺/Fe^III_aqO⁺) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E⁰ (Fe^IV_aqO²⁺, H⁺/Fe^III_aqOH²⁺) ≥ 1.95 V.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1259478

Report Number(s):: IS-J-8983

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 27 works

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