The first photocrystallographic evidence for light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes

Andrey Yu Kovalevsky; Kimberly A. Bagley; Philip Coppens

doi:10.1021/ja026045c

The first photocrystallographic evidence for light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes

Andrey Yu Kovalevsky, Kimberly A. Bagley, Philip Coppens

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106 Scopus citations

Abstract

Light-induced metastable linkage isomers of trans-[Ru(NH₃)₄Cl(SO₂)]Cl and trans-[Ru(NH₃)₄- (H₂O)(SO₂)](C₆H₅ SO₃)₂ have been identified for the first time using photocrystallographic methods. In both linkage isomers the SO₂ ligand is side bound, but the Ru-O and Ru-S distances are considerably longer and almost equal in the trans-H₂O isomer. DFT calculations confirm that both isomers correspond to minima on the ground-state potential energy surface and also predict the existence of a second oxygen-bound isomer for both compounds. The decay of the light-induced species has been studied by both DSC and IR. Activation energies for the thermal back-reaction, as derived from the temperature-dependent disappearance of light-induced IR bands, are 50.0 and 58.4 kJ/mol for the two isomers, which is larger than the corresponding numbers for photoinduced side-bound nitrosyl linkage isomers.

Original language	English
Pages (from-to)	9241-9248
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	124
Issue number	31
DOIs	https://doi.org/10.1021/ja026045c
State	Published - Aug 7 2002
Externally published	Yes

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title = "The first photocrystallographic evidence for light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes",

abstract = "Light-induced metastable linkage isomers of trans-[Ru(NH3)4Cl(SO2)]Cl and trans-[Ru(NH3)4- (H2O)(SO2)](C6H5 SO3)2 have been identified for the first time using photocrystallographic methods. In both linkage isomers the SO2 ligand is side bound, but the Ru-O and Ru-S distances are considerably longer and almost equal in the trans-H2O isomer. DFT calculations confirm that both isomers correspond to minima on the ground-state potential energy surface and also predict the existence of a second oxygen-bound isomer for both compounds. The decay of the light-induced species has been studied by both DSC and IR. Activation energies for the thermal back-reaction, as derived from the temperature-dependent disappearance of light-induced IR bands, are 50.0 and 58.4 kJ/mol for the two isomers, which is larger than the corresponding numbers for photoinduced side-bound nitrosyl linkage isomers.",

author = "Kovalevsky, {Andrey Yu} and Bagley, {Kimberly A.} and Philip Coppens",

year = "2002",

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doi = "10.1021/ja026045c",

language = "English",

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journal = "Journal of the American Chemical Society",

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T1 - The first photocrystallographic evidence for light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes

AU - Kovalevsky, Andrey Yu

AU - Bagley, Kimberly A.

AU - Coppens, Philip

PY - 2002/8/7

Y1 - 2002/8/7

N2 - Light-induced metastable linkage isomers of trans-[Ru(NH3)4Cl(SO2)]Cl and trans-[Ru(NH3)4- (H2O)(SO2)](C6H5 SO3)2 have been identified for the first time using photocrystallographic methods. In both linkage isomers the SO2 ligand is side bound, but the Ru-O and Ru-S distances are considerably longer and almost equal in the trans-H2O isomer. DFT calculations confirm that both isomers correspond to minima on the ground-state potential energy surface and also predict the existence of a second oxygen-bound isomer for both compounds. The decay of the light-induced species has been studied by both DSC and IR. Activation energies for the thermal back-reaction, as derived from the temperature-dependent disappearance of light-induced IR bands, are 50.0 and 58.4 kJ/mol for the two isomers, which is larger than the corresponding numbers for photoinduced side-bound nitrosyl linkage isomers.

AB - Light-induced metastable linkage isomers of trans-[Ru(NH3)4Cl(SO2)]Cl and trans-[Ru(NH3)4- (H2O)(SO2)](C6H5 SO3)2 have been identified for the first time using photocrystallographic methods. In both linkage isomers the SO2 ligand is side bound, but the Ru-O and Ru-S distances are considerably longer and almost equal in the trans-H2O isomer. DFT calculations confirm that both isomers correspond to minima on the ground-state potential energy surface and also predict the existence of a second oxygen-bound isomer for both compounds. The decay of the light-induced species has been studied by both DSC and IR. Activation energies for the thermal back-reaction, as derived from the temperature-dependent disappearance of light-induced IR bands, are 50.0 and 58.4 kJ/mol for the two isomers, which is larger than the corresponding numbers for photoinduced side-bound nitrosyl linkage isomers.

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The first photocrystallographic evidence for light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes

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