Multiple Bonds between Main Group Elements and Transition Metals. 144.1 Photoreactivity of Organorhenium(VII) Oxides

Wolfgang A. Herrmann; Fritz E. Kühn; Dirk A. Fiedler; Mike R. Mattner; Martin R. Geisberger; Horst Kunkely; Arnd Vogler; Steen Steenken

doi:10.1021/om00011a064

Multiple Bonds between Main Group Elements and Transition Metals. 144.¹ Photoreactivity of Organorhenium(VII) Oxides

Wolfgang A. Herrmann, Fritz E. Kühn, Dirk A. Fiedler, Mike R. Mattner, Martin R. Geisberger, Horst Kunkely, Arnd Vogler, Steen Steenken

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Abstract

Ligand-to-metal charge transfer excitation of organorhenium(VII) oxides R-ReO₃[R = CH3, C2H5, η¹-mesityl, C₆H₅, η⁵-C₅H₅, η⁵-C₅H₄(CH₃), and η⁵-C₅CCH₃)₅] in acetonitrile or dichloromethane solution leads to photoredox decomposition. It is shown by EPR spectroscopy that radical pairs R•/•ReO₃ are generated in the primary step. The overall efficiency is determined by the reactivity of the radicals R^•, which decreases in the order CH₃ > C₂H₅ > mesityl > C₅H₅ > C5H₄(CH₃) > C₅(CH₃)5. The regeneration of R-ReO₃ is favored with increasing stability of R^•. Accordingly the quantum yield varies with R.

Original language	English
Pages (from-to)	5377-5381
Number of pages	5
Journal	Organometallics
Volume	14
Issue number	11
DOIs	https://doi.org/10.1021/om00011a064
State	Published - Nov 1995

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title = "Multiple Bonds between Main Group Elements and Transition Metals. 144.1 Photoreactivity of Organorhenium(VII) Oxides",

abstract = "Ligand-to-metal charge transfer excitation of organorhenium(VII) oxides R-ReO3[R = CH3, C2H5, η1-mesityl, C6H5, η5-C5H5, η5-C5H4(CH3), and η5-C5CCH3)5] in acetonitrile or dichloromethane solution leads to photoredox decomposition. It is shown by EPR spectroscopy that radical pairs R•/•ReO3 are generated in the primary step. The overall efficiency is determined by the reactivity of the radicals R•, which decreases in the order CH3 > C2H5 > mesityl > C5H5 > C5H4(CH3) > C5(CH3)5. The regeneration of R-ReO3 is favored with increasing stability of R•. Accordingly the quantum yield varies with R.",

author = "Herrmann, {Wolfgang A.} and K{\"u}hn, {Fritz E.} and Fiedler, {Dirk A.} and Mattner, {Mike R.} and Geisberger, {Martin R.} and Horst Kunkely and Arnd Vogler and Steen Steenken",

year = "1995",

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doi = "10.1021/om00011a064",

language = "English",

volume = "14",

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journal = "Organometallics",

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T1 - Multiple Bonds between Main Group Elements and Transition Metals. 144.1 Photoreactivity of Organorhenium(VII) Oxides

AU - Herrmann, Wolfgang A.

AU - Kühn, Fritz E.

AU - Fiedler, Dirk A.

AU - Mattner, Mike R.

AU - Geisberger, Martin R.

AU - Kunkely, Horst

AU - Vogler, Arnd

AU - Steenken, Steen

PY - 1995/11

Y1 - 1995/11

N2 - Ligand-to-metal charge transfer excitation of organorhenium(VII) oxides R-ReO3[R = CH3, C2H5, η1-mesityl, C6H5, η5-C5H5, η5-C5H4(CH3), and η5-C5CCH3)5] in acetonitrile or dichloromethane solution leads to photoredox decomposition. It is shown by EPR spectroscopy that radical pairs R•/•ReO3 are generated in the primary step. The overall efficiency is determined by the reactivity of the radicals R•, which decreases in the order CH3 > C2H5 > mesityl > C5H5 > C5H4(CH3) > C5(CH3)5. The regeneration of R-ReO3 is favored with increasing stability of R•. Accordingly the quantum yield varies with R.

AB - Ligand-to-metal charge transfer excitation of organorhenium(VII) oxides R-ReO3[R = CH3, C2H5, η1-mesityl, C6H5, η5-C5H5, η5-C5H4(CH3), and η5-C5CCH3)5] in acetonitrile or dichloromethane solution leads to photoredox decomposition. It is shown by EPR spectroscopy that radical pairs R•/•ReO3 are generated in the primary step. The overall efficiency is determined by the reactivity of the radicals R•, which decreases in the order CH3 > C2H5 > mesityl > C5H5 > C5H4(CH3) > C5(CH3)5. The regeneration of R-ReO3 is favored with increasing stability of R•. Accordingly the quantum yield varies with R.

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ER -

Multiple Bonds between Main Group Elements and Transition Metals. 144.¹ Photoreactivity of Organorhenium(VII) Oxides

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