Issue 4, 2007

Insertion of CO2 into a palladiumallyl bond and a Pd(ii) catalysed carboxylation of allyl stannanes

Abstract

The complex 2,6-bis[(di-t-butylphosphino)methyl]phenyl allyl palladium (PCPtBuPd-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 γ-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.

Graphical abstract: Insertion of CO2 into a palladium allyl bond and a Pd(ii) catalysed carboxylation of allyl stannanes

Article information

Article type
Paper
Submitted
27 Gwen. 2006
Accepted
28 Du 2006
First published
18 Ker. 2006

Dalton Trans., 2007, 488-492

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

R. Johansson and O. F. Wendt, Dalton Trans., 2007, 488 DOI: 10.1039/B614037H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements