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Insertion of CO2 into a palladium allyl bond and a Pd(II) catalysed carboxylation of allyl stannanes

Johansson, Roger LU and Wendt, Ola LU (2007) In Dalton Transactions p.488-492
Abstract
The complex 2,6-bis[(di-t-butylphosphino)methyl]phenyl allyl palladium ((PCPPd)-Pd-tBu-allyl, 3) reacts with CO2 in a very fast insertion reaction to give the corresponding butenoate complex. The reaction is thought to occur via a cyclic six-membered transition state (7), where the gamma-carbon of the allyl group is linked up with the CO2-carbon. A group of related PCP complexes were investigated as catalysts for the carboxylation of tributyl(allyl) stannane. A catalytic cycle is proposed for this reaction where the rate determining step is the transmetallation between tin and palladium. The carboxylation reaction is faster using less sterically crowded catalysts whereas the electron richness of the palladium complexes seems less important... (More)
The complex 2,6-bis[(di-t-butylphosphino)methyl]phenyl allyl palladium ((PCPPd)-Pd-tBu-allyl, 3) reacts with CO2 in a very fast insertion reaction to give the corresponding butenoate complex. The reaction is thought to occur via a cyclic six-membered transition state (7), where the gamma-carbon of the allyl group is linked up with the CO2-carbon. A group of related PCP complexes were investigated as catalysts for the carboxylation of tributyl(allyl) stannane. A catalytic cycle is proposed for this reaction where the rate determining step is the transmetallation between tin and palladium. The carboxylation reaction is faster using less sterically crowded catalysts whereas the electron richness of the palladium complexes seems less important for reactivity. Thus, there was no apparent difference in reactivity between 2,6-bis[(di-phenylphosphino)methyl]phenyl palladium triflouroacetate (13) and resorcinolbis(diphenyl)phosphinite palladium triflouroacetate (10). Both of these complexes give high turnovers for the carboxylation of tributyl(allyl) stannane (80% in 16 h using a ca. 5% catalyst loading and 4 atm CO2 pressure). On the other hand complex 3 was inactive in the catalytic carboxylation reaction. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Dalton Transactions
issue
4
pages
488 - 492
publisher
Royal Society of Chemistry
external identifiers
  • wos:000243380900014
  • scopus:33846100002
ISSN
1477-9234
DOI
10.1039/b614037h
language
English
LU publication?
yes
id
aa3f67a4-58e4-46bd-a5ca-3a2f2d561426 (old id 679499)
date added to LUP
2007-12-13 13:31:13
date last changed
2017-07-30 03:48:32
@article{aa3f67a4-58e4-46bd-a5ca-3a2f2d561426,
  abstract     = {The complex 2,6-bis[(di-t-butylphosphino)methyl]phenyl allyl palladium ((PCPPd)-Pd-tBu-allyl, 3) reacts with CO2 in a very fast insertion reaction to give the corresponding butenoate complex. The reaction is thought to occur via a cyclic six-membered transition state (7), where the gamma-carbon of the allyl group is linked up with the CO2-carbon. A group of related PCP complexes were investigated as catalysts for the carboxylation of tributyl(allyl) stannane. A catalytic cycle is proposed for this reaction where the rate determining step is the transmetallation between tin and palladium. The carboxylation reaction is faster using less sterically crowded catalysts whereas the electron richness of the palladium complexes seems less important for reactivity. Thus, there was no apparent difference in reactivity between 2,6-bis[(di-phenylphosphino)methyl]phenyl palladium triflouroacetate (13) and resorcinolbis(diphenyl)phosphinite palladium triflouroacetate (10). Both of these complexes give high turnovers for the carboxylation of tributyl(allyl) stannane (80% in 16 h using a ca. 5% catalyst loading and 4 atm CO2 pressure). On the other hand complex 3 was inactive in the catalytic carboxylation reaction.},
  author       = {Johansson, Roger and Wendt, Ola},
  issn         = {1477-9234},
  language     = {eng},
  number       = {4},
  pages        = {488--492},
  publisher    = {Royal Society of Chemistry},
  series       = {Dalton Transactions},
  title        = {Insertion of CO2 into a palladium allyl bond and a Pd(II) catalysed carboxylation of allyl stannanes},
  url          = {http://dx.doi.org/10.1039/b614037h},
  year         = {2007},
}