Photoinduced atom-transfer reactions between transition-metal centres

Carol Creutz; Jeong Sup Song; R. Morris Bullock

doi:10.1351/pac199567010047

Photoinduced atom-transfer reactions between transition-metal centres

Carol Creutz, Jeong Sup Song, R. Morris Bullock

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

In contrast to outer-sphere electron transfer, the intrinsic barriers to redox reactions accomplished by atom-transfer processes have received little attention. We have begun a study of the self-exchange atom transfer process for both two-equivalent and one-equivalent systems. In the former studies, NMR techniques ranging from line broadening to magnetization transfer were used for C₅H₅(CO)₃M^-/C₅H₅(CO)₃M-X self-exchange reactions (M = Mo, W; X = Cl, Br, I). For the one-equivalent processes, we have applied isotopically labeled materials and a photochemical method to the direct determination of the self-exchange rates for C₅H₅(CO)₃M./C₅H₅(CO)₃M-X couples. The metal radicals are produced by photocleavage of metal-metal bonded dimers by visible light.

Original language	English
Pages (from-to)	47-54
Number of pages	8
Journal	Pure and Applied Chemistry
Volume	67
Issue number	1
DOIs	https://doi.org/10.1351/pac199567010047
Publication status	Published - Jan 1 1995

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)

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title = "Photoinduced atom-transfer reactions between transition-metal centres",

abstract = "In contrast to outer-sphere electron transfer, the intrinsic barriers to redox reactions accomplished by atom-transfer processes have received little attention. We have begun a study of the self-exchange atom transfer process for both two-equivalent and one-equivalent systems. In the former studies, NMR techniques ranging from line broadening to magnetization transfer were used for C5H5(CO)3M-/C5H5(CO)3M-X self-exchange reactions (M = Mo, W; X = Cl, Br, I). For the one-equivalent processes, we have applied isotopically labeled materials and a photochemical method to the direct determination of the self-exchange rates for C5H5(CO)3M./C5H5(CO)3M-X couples. The metal radicals are produced by photocleavage of metal-metal bonded dimers by visible light.",

author = "Carol Creutz and Song, {Jeong Sup} and Bullock, {R. Morris}",

note = "Funding Information: We thank Drs. B. S. Brunschwig, H. A. Schwarz, and N. Sutin for invaluable discussions. This research was carried out at Brookhaven National Laboratory under contract DE-AC02-76CH00016 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences.",

year = "1995",

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AU - Creutz, Carol

AU - Song, Jeong Sup

AU - Bullock, R. Morris

N1 - Funding Information: We thank Drs. B. S. Brunschwig, H. A. Schwarz, and N. Sutin for invaluable discussions. This research was carried out at Brookhaven National Laboratory under contract DE-AC02-76CH00016 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences.

PY - 1995/1/1

Y1 - 1995/1/1

N2 - In contrast to outer-sphere electron transfer, the intrinsic barriers to redox reactions accomplished by atom-transfer processes have received little attention. We have begun a study of the self-exchange atom transfer process for both two-equivalent and one-equivalent systems. In the former studies, NMR techniques ranging from line broadening to magnetization transfer were used for C5H5(CO)3M-/C5H5(CO)3M-X self-exchange reactions (M = Mo, W; X = Cl, Br, I). For the one-equivalent processes, we have applied isotopically labeled materials and a photochemical method to the direct determination of the self-exchange rates for C5H5(CO)3M./C5H5(CO)3M-X couples. The metal radicals are produced by photocleavage of metal-metal bonded dimers by visible light.

AB - In contrast to outer-sphere electron transfer, the intrinsic barriers to redox reactions accomplished by atom-transfer processes have received little attention. We have begun a study of the self-exchange atom transfer process for both two-equivalent and one-equivalent systems. In the former studies, NMR techniques ranging from line broadening to magnetization transfer were used for C5H5(CO)3M-/C5H5(CO)3M-X self-exchange reactions (M = Mo, W; X = Cl, Br, I). For the one-equivalent processes, we have applied isotopically labeled materials and a photochemical method to the direct determination of the self-exchange rates for C5H5(CO)3M./C5H5(CO)3M-X couples. The metal radicals are produced by photocleavage of metal-metal bonded dimers by visible light.

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