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Kinetic investigation of a PC(sp(3))P pincer palladium (II) complex in the Heck reaction

Nilsson, Patrik LU and Wendt, Ola LU (2005) In Journal of Organometallic Chemistry 690(18). p.4197-4202
Abstract
An investigation of the kinetics of the Heck reaction between 4-iodoanisole and styrene catalysed by {cis-1,3-bis[(di-tert-butylphosphino)methyl]-cyclohexane} palladium (11) iodide (1) has been performed in DMF-d(7) solution. Based on mercury poisoning experiments a heterogeneous palladium catalyst formed from the PCsp3P Pd(II) pre-catalyst is proposed. Saturation behaviour with respect to the olefin concentration suggests a mechanism consisting of a pre-equilibrium association of the olefin followed by a rate determining reaction with aryl halide. The equilibrium constant for the olefin association, K-1, and the rate constant for the subsequent oxidative addition step, k(2), were determined to (5.7 +/- 2.5) x 10(-3) and 18.4 +/- 2.7 M-1... (More)
An investigation of the kinetics of the Heck reaction between 4-iodoanisole and styrene catalysed by {cis-1,3-bis[(di-tert-butylphosphino)methyl]-cyclohexane} palladium (11) iodide (1) has been performed in DMF-d(7) solution. Based on mercury poisoning experiments a heterogeneous palladium catalyst formed from the PCsp3P Pd(II) pre-catalyst is proposed. Saturation behaviour with respect to the olefin concentration suggests a mechanism consisting of a pre-equilibrium association of the olefin followed by a rate determining reaction with aryl halide. The equilibrium constant for the olefin association, K-1, and the rate constant for the subsequent oxidative addition step, k(2), were determined to (5.7 +/- 2.5) x 10(-3) and 18.4 +/- 2.7 M-1 s(-1), respectively. (c) 2005 Elsevier B.V. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Organometallic Chemistry
volume
690
issue
18
pages
4197 - 4202
publisher
Elsevier
external identifiers
  • wos:000231995700013
  • scopus:25444434697
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2005.06.014
language
English
LU publication?
yes
id
50bf97a3-77f1-4369-9f77-d06a64e3058b (old id 152325)
date added to LUP
2007-07-10 13:21:12
date last changed
2017-01-01 06:55:33
@article{50bf97a3-77f1-4369-9f77-d06a64e3058b,
  abstract     = {An investigation of the kinetics of the Heck reaction between 4-iodoanisole and styrene catalysed by {cis-1,3-bis[(di-tert-butylphosphino)methyl]-cyclohexane} palladium (11) iodide (1) has been performed in DMF-d(7) solution. Based on mercury poisoning experiments a heterogeneous palladium catalyst formed from the PCsp3P Pd(II) pre-catalyst is proposed. Saturation behaviour with respect to the olefin concentration suggests a mechanism consisting of a pre-equilibrium association of the olefin followed by a rate determining reaction with aryl halide. The equilibrium constant for the olefin association, K-1, and the rate constant for the subsequent oxidative addition step, k(2), were determined to (5.7 +/- 2.5) x 10(-3) and 18.4 +/- 2.7 M-1 s(-1), respectively. (c) 2005 Elsevier B.V. All rights reserved.},
  author       = {Nilsson, Patrik and Wendt, Ola},
  issn         = {0022-328X},
  language     = {eng},
  number       = {18},
  pages        = {4197--4202},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {Kinetic investigation of a PC(sp(3))P pincer palladium (II) complex in the Heck reaction},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2005.06.014},
  volume       = {690},
  year         = {2005},
}