Citation
Zh. Qu et al., A kinetic study on the pairwise competition reaction of alpha-diazo esterswith rhodium(II) catalysts: Implication for the mechanism of Rh(II)-carbene transfer, J ORG CHEM, 66(24), 2001, pp. 8139-8144
Citations number
40
Categorie Soggetti
Chemistry & Analysis","Organic Chemistry/Polymer Science
Journal title
JOURNAL OF ORGANIC CHEMISTRY
ISSN journal
00223263
→ ACNP
Volume
66
Issue
24
Year of publication
2001
Pages
8139 - 8144
Database
ISI
SICI code
0022-3263(20011130)66:24<8139:AKSOTP>2.0.ZU;2-Q
Abstract
The relative rate constants for the Rh(II)-mediated diazo decomposition of
a series of para- or meta-substituted diazophenylacetates were measured thr
ough intermolecular competition. The kinetic data were further subjected to
Hammett correlation analysis and were found to have better linear correlat
ion with sigma (+). Reaction constants for four Rh(II) catalysts have been
obtained, Rh-2(OAc)(4) (rho = -1.29 with sigma (+), r = -0.99), Rh-2(Ooct)(
4) (rho = -1.31 with sigma (+), r = -0.99), Rh-2(acam)(4) (rho = -1.18 with
sigma (+), r = -0.99), Rh-2(O2CCF3)(4) (rho = -1.46 with sigma (+), r = -0
.99). The mechanistic implications of these data are discussed.