Some Mechanistic Evidence for an Oxygen Transfer Reaction Accompanied by the Redox-Induced Nitrito-Nitro Linkage Isomerization of Ruthenium Complex Having Nitrosyl, cis-[Ru(NO)(X)(bpy)2]2+ (X = ONO, NO2)

Dai Ooyama; Hirotaka Nagao; Noriharu Nagao; F. Scott Howell; Masao Mukaida

doi:10.1246/cl.1996.759

September 1, 1996Chemistry Letters

Some Mechanistic Evidence for an Oxygen Transfer Reaction Accompanied by the Redox-Induced Nitrito-Nitro Linkage Isomerization of Ruthenium Complex Having Nitrosyl, cis-[Ru(NO)(X)(bpy)2]2+ (X = ONO, NO2)

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Key Points

To investigate the mechanism of ligand transformation and potential oxygen transfer during the redox-induced nitrito-to-nitro linkage isomerization in a ruthenium nitrosyl complex.
Evaluated the reaction mechanism during the redox-induced isomerization of cis-[Ru(NO)(ONO)(bpy)2]2+ to its nitro isomer.
Compared reaction pathways between redox-induced and thermally-induced linkage isomerization.
An intramolecular oxygen transfer occurs directly between the nitrosyl (NO) and nitrito (ONO) ligands during redox-induced isomerization of cis-[Ru(NO)(ONO)(bpy)2]2+.
Oxygen transfer is absent in the previously reported thermally-induced linkage isomerization of the same complex.

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Implication

Mechanistic analysis reveals oxygen transfer between ligands in cis-[Ru(NO)(ONO)(bpy)2]2+ during redox isomerization, indicating a mechanism distinct from thermal pathways.

Abstract

An oxygen transfer between the NO and the ONO ligands occurs in cis-[Ru(NO)(ONO)(bpy)2]2+ when the complex undergoes a redox-induced nitrito-to-nitro linkage isomerization. Such an oxygen transfer does not occur in a themally-induced linkage isomerization reported previously.

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Ooyama et al. (1996) studied this question.

synapsesocial.com/papers/6a9fe4028757c75042ec79ee https://doi.org/10.1246/cl.1996.759

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Some Mechanistic Evidence for an Oxygen Transfer Reaction Accompanied by the Redox-Induced Nitrito-Nitro Linkage Isomerization of Ruthenium Complex Having Nitrosyl, cis-[Ru(NO)(X)(bpy)2]2+ (X = ONO, NO2)

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Some Mechanistic Evidence for an Oxygen Transfer Reaction Accompanied by the Redox-Induced Nitrito-Nitro Linkage Isomerization of Ruthenium Complex Having Nitrosyl, cis-[Ru(NO)(X)(bpy)2]2+ (X = ONO, NO2)

Key Points

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Abstract

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