Insertion of CO2 into a palladium allyl bond and a Pd(II) catalysed carboxylation of allyl stannanes
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/679499
- author
- Johansson, Roger LU and Wendt, Ola LU
- organization
- publishing date
- 2007
- 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
- pmid:17213935
- ISSN
- 1477-9234
- DOI
- 10.1039/b614037h
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)
- id
- aa3f67a4-58e4-46bd-a5ca-3a2f2d561426 (old id 679499)
- date added to LUP
- 2016-04-01 12:21:05
- date last changed
- 2022-03-28 23:40:47
@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}},
doi = {{10.1039/b614037h}},
year = {{2007}},
}