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19-electron intermediates in the Ligand Substitution of CpW(CO)3with a Lewis Base [electronic resource].

Published
Arlington, Va. : National Science Foundation (U.S.), 2005.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Additional Creators
National Science Foundation (U.S.) and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
Odd electron species are important intermediates in organometallic chemistry, participating in a variety of catalytic and electron-transfer reactions which produce stable even-electron products. While electron deficient 17-electron (17e) radicals have been well characterized, the possible existence of short-lived 19-electron (19e) radicals has been a subject of continuing investigation. 19e radicals have been postulated as intermediates in the photochemical ligand substitution and disproportionation reactions of organometallic dimers containing a single metal-metal bond, yet the reactions of these intermediates on diffusion-limited time scales (ns-{micro}s) have never been directly observed. This study resolves the 19e dynamics in the ligand substitution of 17e radicals CpW(CO)₃{sup {sm_bullet}} (Cp = C₅H₅) with the Lewis base P(OMe)₃, providing the first complete description 19e reactivity.
Report Numbers
E 1.99:lbnl--59215
lbnl--59215
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Note
Published through SciTech Connect.
12/14/2005.
"lbnl--59215"
": KC0301020"
Journal of the American Chemical Society 128 10 ISSN 0002-7863; JACSAT FT
Frei,Heinz; Harris, Charles B.; Kling, Matthias F.; Cahoon, James F.; Sawyer, Karma R.
Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
Alexander von HumboldtFoundation
Funding Information
DE-AC02-05CH11231
4005
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