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Title: 19-electron intermediates in the Ligand Substitution of CpW(CO)3with a Lewis Base

Abstract

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){sub 3}{sup {sm_bullet}} (Cp = C{sub 5}H{sub 5}) with the Lewis base P(OMe){sub 3}, providing the first complete description 19e reactivity.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
Sponsoring Org.:
USDOE Director. Office of Science. Office of Basic EnergySciences. Chemical Sciences Geosciences and Biosciences Division; National Science Foundation (NSF); Alexander von HumboldtFoundation
OSTI Identifier:
891214
Report Number(s):
LBNL-59215
Journal ID: ISSN 0002-7863; JACSAT; R&D Project: 4005; BnR: KC0301020; TRN: US200621%%675
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 128; Journal Issue: 10; Related Information: Journal Publication Date: 03/15/2006
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMISTRY; DIMERS; ELECTRON TRANSFER; ELECTRONS; LEWIS BASES; OXIDATION; RADICALS; REDUCTION; electronligandLewis base

Citation Formats

Cahoon, James F., Kling, Matthias F., Sawyer, Karma R., Frei,Heinz, and Harris, Charles B. 19-electron intermediates in the Ligand Substitution of CpW(CO)3with a Lewis Base. United States: N. p., 2005. Web.
Cahoon, James F., Kling, Matthias F., Sawyer, Karma R., Frei,Heinz, & Harris, Charles B. 19-electron intermediates in the Ligand Substitution of CpW(CO)3with a Lewis Base. United States.
Cahoon, James F., Kling, Matthias F., Sawyer, Karma R., Frei,Heinz, and Harris, Charles B. Wed . "19-electron intermediates in the Ligand Substitution of CpW(CO)3with a Lewis Base". United States. doi:. https://www.osti.gov/servlets/purl/891214.
@article{osti_891214,
title = {19-electron intermediates in the Ligand Substitution of CpW(CO)3with a Lewis Base},
author = {Cahoon, James F. and Kling, Matthias F. and Sawyer, Karma R. and Frei,Heinz and Harris, Charles B.},
abstractNote = {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){sub 3}{sup {sm_bullet}} (Cp = C{sub 5}H{sub 5}) with the Lewis base P(OMe){sub 3}, providing the first complete description 19e reactivity.},
doi = {},
journal = {Journal of the American Chemical Society},
number = 10,
volume = 128,
place = {United States},
year = {Wed Dec 14 00:00:00 EST 2005},
month = {Wed Dec 14 00:00:00 EST 2005}
}