Electrochemical Oxidation of Tetrakis (1, 8-diisocyanomenthane) dirhodium (2+) in Nonaqueous Solutions: A Net Two-Electron Oxidation Process

Matthew R. Rhodes; Kent R Mann

doi:10.1021/ic00182a015

Electrochemical Oxidation of Tetrakis (1, 8-diisocyanomenthane) dirhodium (2+) in Nonaqueous Solutions: A Net Two-Electron Oxidation Process

Matthew R. Rhodes, Kent R Mann

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31 Scopus citations

Abstract

The electrochemical behavior of [Rh₂(dimen)₄]²⁺ (dimen = 1,8-diisocyanomenthane) in the nonaqueous solvents CH₃CN and CH₂Cl₂has been investigated by cyclic voltammetry, potential-step methods, and double-potential-step chronocoulometry. The appearance of the cyclic voltammogram is dramatically influenced by relatively weak ionic aggregation of the [Rh₂(dimen)₄]²⁺ species with the supporting anion and by the strong complexation of the 2e oxidized species [Rh₂(dimen)₄]⁴⁺ formed at the electrode. The formal 2e couple E°'_4+/2+in CH₂Cl₂solutions in the presence of ClO₄^- is +0.46 V vs. Ag/AgCl. The relative stabilities of the 2e oxidized species [Rh₂(dimen)₄(X)₂]²⁺ (X = PF₆^-, ClO₄^-, and Cl^-) are estimated. The Cl^- and ClO₄^- complexes are respectively 46.6 and 4.6 kcal/mol more stable than the corresponding PF₆^- complex. The differences in the behavior of the [Rh₂(dimen)₄]²⁺ system studied here are compared to the previously studied [Rh₂(bridge)₄]²⁺ system.

Original language	English (US)
Pages (from-to)	2053-2058
Number of pages	6
Journal	Inorganic chemistry
Volume	23
Issue number	14
DOIs	https://doi.org/10.1021/ic00182a015
State	Published - Jan 1984
Externally published	Yes

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title = "Electrochemical Oxidation of Tetrakis (1, 8-diisocyanomenthane) dirhodium (2+) in Nonaqueous Solutions: A Net Two-Electron Oxidation Process",

abstract = "The electrochemical behavior of [Rh2(dimen)4]2+ (dimen = 1,8-diisocyanomenthane) in the nonaqueous solvents CH3CN and CH2Cl2has been investigated by cyclic voltammetry, potential-step methods, and double-potential-step chronocoulometry. The appearance of the cyclic voltammogram is dramatically influenced by relatively weak ionic aggregation of the [Rh2(dimen)4]2+ species with the supporting anion and by the strong complexation of the 2e oxidized species [Rh2(dimen)4]4+ formed at the electrode. The formal 2e couple E°'4+/2+in CH2Cl2solutions in the presence of ClO4- is +0.46 V vs. Ag/AgCl. The relative stabilities of the 2e oxidized species [Rh2(dimen)4(X)2]2+ (X = PF6-, ClO4-, and Cl-) are estimated. The Cl- and ClO4- complexes are respectively 46.6 and 4.6 kcal/mol more stable than the corresponding PF6- complex. The differences in the behavior of the [Rh2(dimen)4]2+ system studied here are compared to the previously studied [Rh2(bridge)4]2+ system.",

author = "Rhodes, {Matthew R.} and Mann, {Kent R}",

year = "1984",

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T2 - A Net Two-Electron Oxidation Process

AU - Rhodes, Matthew R.

AU - Mann, Kent R

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N2 - The electrochemical behavior of [Rh2(dimen)4]2+ (dimen = 1,8-diisocyanomenthane) in the nonaqueous solvents CH3CN and CH2Cl2has been investigated by cyclic voltammetry, potential-step methods, and double-potential-step chronocoulometry. The appearance of the cyclic voltammogram is dramatically influenced by relatively weak ionic aggregation of the [Rh2(dimen)4]2+ species with the supporting anion and by the strong complexation of the 2e oxidized species [Rh2(dimen)4]4+ formed at the electrode. The formal 2e couple E°'4+/2+in CH2Cl2solutions in the presence of ClO4- is +0.46 V vs. Ag/AgCl. The relative stabilities of the 2e oxidized species [Rh2(dimen)4(X)2]2+ (X = PF6-, ClO4-, and Cl-) are estimated. The Cl- and ClO4- complexes are respectively 46.6 and 4.6 kcal/mol more stable than the corresponding PF6- complex. The differences in the behavior of the [Rh2(dimen)4]2+ system studied here are compared to the previously studied [Rh2(bridge)4]2+ system.

AB - The electrochemical behavior of [Rh2(dimen)4]2+ (dimen = 1,8-diisocyanomenthane) in the nonaqueous solvents CH3CN and CH2Cl2has been investigated by cyclic voltammetry, potential-step methods, and double-potential-step chronocoulometry. The appearance of the cyclic voltammogram is dramatically influenced by relatively weak ionic aggregation of the [Rh2(dimen)4]2+ species with the supporting anion and by the strong complexation of the 2e oxidized species [Rh2(dimen)4]4+ formed at the electrode. The formal 2e couple E°'4+/2+in CH2Cl2solutions in the presence of ClO4- is +0.46 V vs. Ag/AgCl. The relative stabilities of the 2e oxidized species [Rh2(dimen)4(X)2]2+ (X = PF6-, ClO4-, and Cl-) are estimated. The Cl- and ClO4- complexes are respectively 46.6 and 4.6 kcal/mol more stable than the corresponding PF6- complex. The differences in the behavior of the [Rh2(dimen)4]2+ system studied here are compared to the previously studied [Rh2(bridge)4]2+ system.

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Electrochemical Oxidation of Tetrakis (1, 8-diisocyanomenthane) dirhodium (2+) in Nonaqueous Solutions: A Net Two-Electron Oxidation Process

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