Homolytic Decomposition of Tertiary Organochromium(III) Complexes and Evidence for Their Decomposition via Reactions with Aliphatic Free Radicals. A Pulse Radiolysis Study

William A. Mulac; Haim Cohen; Dan Meyerstein

doi:10.1021/ic00141a028

Homolytic Decomposition of Tertiary Organochromium(III) Complexes and Evidence for Their Decomposition via Reactions with Aliphatic Free Radicals. A Pulse Radiolysis Study

William A. Mulac, Haim Cohen, Dan Meyerstein

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Abstract

The rates of homolytic decomposition of Cr-C(CH₃)₂OH²⁺, Cr-C(CH₃)₂CO₂H²⁺, and Cr-C(CH₃)₂CN²⁺ are 0.15 s⁻¹, 4 s⁻¹, and 10⁴ < k < 10⁶ s⁻¹, respectively. The reaction of some aliphatic free radicals, ·R with Cr^III-R complexes is very fast, k₃ ≥ 10⁸ M⁻¹ s⁻¹. The rate of reaction of Cr²⁺(aq) with H₂O₂ is k₁₆ = (3.7 ± 0.7) × 10⁴ M⁻¹ s⁻¹ in good accord with the literature value. These results are discussed in detail.

Original language	English
Pages (from-to)	4016-4020
Number of pages	5
Journal	Inorganic Chemistry
Volume	21
Issue number	11
DOIs	https://doi.org/10.1021/ic00141a028
State	Published - 1982
Externally published	Yes

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title = "Homolytic Decomposition of Tertiary Organochromium(III) Complexes and Evidence for Their Decomposition via Reactions with Aliphatic Free Radicals. A Pulse Radiolysis Study",

abstract = "The rates of homolytic decomposition of Cr-C(CH3)2OH2+, Cr-C(CH3)2CO2H2+, and Cr-C(CH3)2CN2+ are 0.15 s−1, 4 s−1, and 104 < k < 106 s−1, respectively. The reaction of some aliphatic free radicals, ·R with CrIII-R complexes is very fast, k3 ≥ 108 M−1 s−1. The rate of reaction of Cr2+(aq) with H2O2 is k16 = (3.7 ± 0.7) × 104 M−1 s−1 in good accord with the literature value. These results are discussed in detail.",

author = "Mulac, {William A.} and Haim Cohen and Dan Meyerstein",

year = "1982",

doi = "10.1021/ic00141a028",

language = "אנגלית",

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journal = "Inorganic Chemistry",

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T1 - Homolytic Decomposition of Tertiary Organochromium(III) Complexes and Evidence for Their Decomposition via Reactions with Aliphatic Free Radicals. A Pulse Radiolysis Study

AU - Mulac, William A.

AU - Cohen, Haim

AU - Meyerstein, Dan

PY - 1982

Y1 - 1982

N2 - The rates of homolytic decomposition of Cr-C(CH3)2OH2+, Cr-C(CH3)2CO2H2+, and Cr-C(CH3)2CN2+ are 0.15 s−1, 4 s−1, and 104 < k < 106 s−1, respectively. The reaction of some aliphatic free radicals, ·R with CrIII-R complexes is very fast, k3 ≥ 108 M−1 s−1. The rate of reaction of Cr2+(aq) with H2O2 is k16 = (3.7 ± 0.7) × 104 M−1 s−1 in good accord with the literature value. These results are discussed in detail.

AB - The rates of homolytic decomposition of Cr-C(CH3)2OH2+, Cr-C(CH3)2CO2H2+, and Cr-C(CH3)2CN2+ are 0.15 s−1, 4 s−1, and 104 < k < 106 s−1, respectively. The reaction of some aliphatic free radicals, ·R with CrIII-R complexes is very fast, k3 ≥ 108 M−1 s−1. The rate of reaction of Cr2+(aq) with H2O2 is k16 = (3.7 ± 0.7) × 104 M−1 s−1 in good accord with the literature value. These results are discussed in detail.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

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Homolytic Decomposition of Tertiary Organochromium(III) Complexes and Evidence for Their Decomposition via Reactions with Aliphatic Free Radicals. A Pulse Radiolysis Study

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