Properties of the Oxo/Aquo System (bpy)2(py)RuO2+/(bpy)2(py)Ru(OH2)2+

Bruce A. Moyer; Thomas J. Meyer

doi:10.1021/ic50216a024

Properties of the Oxo/Aquo System (bpy)₂(py)RuO²⁺/(bpy)₂(py)Ru(OH₂)²⁺

Bruce A. Moyer
, Thomas J. Meyer

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

265 Scopus citations

Abstract

The complex Ru(bpy)₂(py)H₂O²⁺ (bpy is 2,2'-bipyridine; py is pyridine) has been prepared and found to undergo two reversible one-electron oxidations both by electrochemical means and by redox titrations using Ce(IV). The one-electron oxidation product, Ru(bpy)₂(py)H₂O³⁺, has strongly enchanced properties as an acid, pK_a = 0.85 ± 0.03 at 25.0 °C, I = 1.0 M, compared to the Ru(II) complex, pK_a = 10.79 ± 0.01. The hydroxy complex, Ru(bpy)₂(py)OH²⁺, has also been isolated and characterized as its perchlorate salt. The two-electron product, Ru(bpy)₂(py)O²⁺, was shown to be a Ru(IV)-oxo complex by the results of a series of experiments including elemental analysis, solution conductivity, magnetism, and 180 labeling. Given the acid-base properties of the complexes, redox potentials for the Ru(IV)/Ru(III) and Ru(III)/Ru(II) couples have the expected pH dependences, and at pH 7 the potentials are (vs. the SCE) (bpy)₂(py)RuO²⁺ (bpy)₂(py)RuOH²⁺ (bpy)₂(py)RuOH₂²⁺. Our ability to isolate a stable Ru(IV)-oxo complex and the general redox characteristics of the system are discussed in the context of the oxidation of water, the reduction of oxygen, and the competitive formation of oxo-bridged dimers.

Original language	English
Pages (from-to)	436-444
Number of pages	9
Journal	Inorganic Chemistry
Volume	20
Issue number	2
DOIs	https://doi.org/10.1021/ic50216a024
State	Published - Feb 1981
Externally published	Yes

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@article{ab841353a59c450682639ae4094b4af3,

title = "Properties of the Oxo/Aquo System (bpy)2(py)RuO2+/(bpy)2(py)Ru(OH2)2+",

abstract = "The complex Ru(bpy)2(py)H2O2+ (bpy is 2,2'-bipyridine; py is pyridine) has been prepared and found to undergo two reversible one-electron oxidations both by electrochemical means and by redox titrations using Ce(IV). The one-electron oxidation product, Ru(bpy)2(py)H2O3+, has strongly enchanced properties as an acid, pKa = 0.85 ± 0.03 at 25.0 °C, I = 1.0 M, compared to the Ru(II) complex, pKa = 10.79 ± 0.01. The hydroxy complex, Ru(bpy)2(py)OH2+, has also been isolated and characterized as its perchlorate salt. The two-electron product, Ru(bpy)2(py)O2+, was shown to be a Ru(IV)-oxo complex by the results of a series of experiments including elemental analysis, solution conductivity, magnetism, and 180 labeling. Given the acid-base properties of the complexes, redox potentials for the Ru(IV)/Ru(III) and Ru(III)/Ru(II) couples have the expected pH dependences, and at pH 7 the potentials are (vs. the SCE) (bpy)2(py)RuO2+ (bpy)2(py)RuOH2+ (bpy)2(py)RuOH22+. Our ability to isolate a stable Ru(IV)-oxo complex and the general redox characteristics of the system are discussed in the context of the oxidation of water, the reduction of oxygen, and the competitive formation of oxo-bridged dimers.",

author = "Moyer, \{Bruce A.\} and Meyer, \{Thomas J.\}",

year = "1981",

month = feb,

doi = "10.1021/ic50216a024",

language = "English",

volume = "20",

pages = "436--444",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "2",

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T1 - Properties of the Oxo/Aquo System (bpy)2(py)RuO2+/(bpy)2(py)Ru(OH2)2+

AU - Moyer, Bruce A.

AU - Meyer, Thomas J.

PY - 1981/2

Y1 - 1981/2

N2 - The complex Ru(bpy)2(py)H2O2+ (bpy is 2,2'-bipyridine; py is pyridine) has been prepared and found to undergo two reversible one-electron oxidations both by electrochemical means and by redox titrations using Ce(IV). The one-electron oxidation product, Ru(bpy)2(py)H2O3+, has strongly enchanced properties as an acid, pKa = 0.85 ± 0.03 at 25.0 °C, I = 1.0 M, compared to the Ru(II) complex, pKa = 10.79 ± 0.01. The hydroxy complex, Ru(bpy)2(py)OH2+, has also been isolated and characterized as its perchlorate salt. The two-electron product, Ru(bpy)2(py)O2+, was shown to be a Ru(IV)-oxo complex by the results of a series of experiments including elemental analysis, solution conductivity, magnetism, and 180 labeling. Given the acid-base properties of the complexes, redox potentials for the Ru(IV)/Ru(III) and Ru(III)/Ru(II) couples have the expected pH dependences, and at pH 7 the potentials are (vs. the SCE) (bpy)2(py)RuO2+ (bpy)2(py)RuOH2+ (bpy)2(py)RuOH22+. Our ability to isolate a stable Ru(IV)-oxo complex and the general redox characteristics of the system are discussed in the context of the oxidation of water, the reduction of oxygen, and the competitive formation of oxo-bridged dimers.

AB - The complex Ru(bpy)2(py)H2O2+ (bpy is 2,2'-bipyridine; py is pyridine) has been prepared and found to undergo two reversible one-electron oxidations both by electrochemical means and by redox titrations using Ce(IV). The one-electron oxidation product, Ru(bpy)2(py)H2O3+, has strongly enchanced properties as an acid, pKa = 0.85 ± 0.03 at 25.0 °C, I = 1.0 M, compared to the Ru(II) complex, pKa = 10.79 ± 0.01. The hydroxy complex, Ru(bpy)2(py)OH2+, has also been isolated and characterized as its perchlorate salt. The two-electron product, Ru(bpy)2(py)O2+, was shown to be a Ru(IV)-oxo complex by the results of a series of experiments including elemental analysis, solution conductivity, magnetism, and 180 labeling. Given the acid-base properties of the complexes, redox potentials for the Ru(IV)/Ru(III) and Ru(III)/Ru(II) couples have the expected pH dependences, and at pH 7 the potentials are (vs. the SCE) (bpy)2(py)RuO2+ (bpy)2(py)RuOH2+ (bpy)2(py)RuOH22+. Our ability to isolate a stable Ru(IV)-oxo complex and the general redox characteristics of the system are discussed in the context of the oxidation of water, the reduction of oxygen, and the competitive formation of oxo-bridged dimers.

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U2 - 10.1021/ic50216a024

DO - 10.1021/ic50216a024

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AN - SCOPUS:0001753253

SN - 0020-1669

VL - 20

SP - 436

EP - 444

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 2

ER -

Properties of the Oxo/Aquo System (bpy)₂(py)RuO²⁺/(bpy)₂(py)Ru(OH₂)²⁺

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