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The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts

The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts
The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts
A range of complexes of the formula [PdCl2{P(OAr)(3)}(2)] have been synthesized in order to determine the effect of steric bulk on stereochemistry, one example [PdCl2{P(OC6H4-2-Bu-t)(3)}(2)] has been structurally characterized. Three palladacyclic complexes [{Pd(mu-Cl)-(kappa(2)-P, C-P(OC6H3R)(OC6H4R)(2))}(2)] have been synthesized (R = H, 2-Pr-t, 2-Bu-t) and two have been characterized by crystallography (R = H and Bu-t). The latter adopts the expected trans geometry while the former is cis. In this case, the driving force for the cis geometry seems to be intermolecular interactions in the crystal structure which are disrupted on substitution. We also report an unusual solvolysis reaction.
palladium, phosphite, palladacycle, orthometallation high-activity catalysts, highly-active catalysts, aryl chlorides, efficient catalysts, phosphite complexes, coupling reactions, carbene adducts, suzuki reaction
0277-5387
1003-1010
Bedford, Robin B.
42532c45-cb80-48cd-9e93-8c2d5059eabe
Betham, Michael
0cd66656-1b0f-40b4-8dc7-a7b3121257f6
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
López-Sáez, María-José
0ee0f37e-7811-4aa1-8c90-3e8712b976d5
Bedford, Robin B.
42532c45-cb80-48cd-9e93-8c2d5059eabe
Betham, Michael
0cd66656-1b0f-40b4-8dc7-a7b3121257f6
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
López-Sáez, María-José
0ee0f37e-7811-4aa1-8c90-3e8712b976d5

Bedford, Robin B., Betham, Michael, Coles, Simon J., Horton, Peter N. and López-Sáez, María-José (2006) The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts. Polyhedron, 25 (4), 1003-1010. (doi:10.1016/j.poly.2005.11.014).

Record type: Article

Abstract

A range of complexes of the formula [PdCl2{P(OAr)(3)}(2)] have been synthesized in order to determine the effect of steric bulk on stereochemistry, one example [PdCl2{P(OC6H4-2-Bu-t)(3)}(2)] has been structurally characterized. Three palladacyclic complexes [{Pd(mu-Cl)-(kappa(2)-P, C-P(OC6H3R)(OC6H4R)(2))}(2)] have been synthesized (R = H, 2-Pr-t, 2-Bu-t) and two have been characterized by crystallography (R = H and Bu-t). The latter adopts the expected trans geometry while the former is cis. In this case, the driving force for the cis geometry seems to be intermolecular interactions in the crystal structure which are disrupted on substitution. We also report an unusual solvolysis reaction.

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More information

Published date: 2006
Keywords: palladium, phosphite, palladacycle, orthometallation high-activity catalysts, highly-active catalysts, aryl chlorides, efficient catalysts, phosphite complexes, coupling reactions, carbene adducts, suzuki reaction

Identifiers

Local EPrints ID: 44381
URI: https://eprints.soton.ac.uk/id/eprint/44381
ISSN: 0277-5387
PURE UUID: 7c9bb1e8-e9a0-48c0-97f1-dd84f363b036
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016

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Date deposited: 01 Mar 2007
Last modified: 14 Mar 2019 01:48

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Contributors

Author: Robin B. Bedford
Author: Michael Betham
Author: Simon J. Coles ORCID iD
Author: Peter N. Horton ORCID iD
Author: María-José López-Sáez

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