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Reactivity of iso-diiodomethane and iso-iodoform, isomers of CH2I2 and CHI3, toward the double bond of a variety of cycloalkenes

Tarnovsky, Alexander LU ; Pascher, Irmin and Pascher, Torbjörn LU (2007) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 111(46). p.11814-11817
Abstract
The metastable CH2I-I and CHI2-I isomers formed by UV photolysis of CH2I2, and CHI3 transfer methylene and iodomethylene groups, respectively, to a variety of cycloalkenes, leading to their cyclopropanation. More than a 100-fold increase of the reaction rate with increasing solvent polarity suggests a dipolar transition state. The fastest second-order rates observed were in CH3CN. However, CH2Cl2 will be the more appropriate reaction medium because the isomer thermal stability is greater in CH2Cl2 than in the more polar CH3CN.
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
111
issue
46
pages
11814 - 11817
publisher
The American Chemical Society
external identifiers
  • wos:000250967800011
  • scopus:37049003727
ISSN
1520-5215
DOI
10.1021/jp073917u
language
English
LU publication?
yes
id
c8cf1c67-545b-47c4-b5a3-e90f3f233fbc (old id 971868)
date added to LUP
2008-01-30 09:14:06
date last changed
2017-01-01 07:15:14
@article{c8cf1c67-545b-47c4-b5a3-e90f3f233fbc,
  abstract     = {The metastable CH2I-I and CHI2-I isomers formed by UV photolysis of CH2I2, and CHI3 transfer methylene and iodomethylene groups, respectively, to a variety of cycloalkenes, leading to their cyclopropanation. More than a 100-fold increase of the reaction rate with increasing solvent polarity suggests a dipolar transition state. The fastest second-order rates observed were in CH3CN. However, CH2Cl2 will be the more appropriate reaction medium because the isomer thermal stability is greater in CH2Cl2 than in the more polar CH3CN.},
  author       = {Tarnovsky, Alexander and Pascher, Irmin and Pascher, Torbjörn},
  issn         = {1520-5215},
  language     = {eng},
  number       = {46},
  pages        = {11814--11817},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Reactivity of iso-diiodomethane and iso-iodoform, isomers of CH2I2 and CHI3, toward the double bond of a variety of cycloalkenes},
  url          = {http://dx.doi.org/10.1021/jp073917u},
  volume       = {111},
  year         = {2007},
}