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Synthesis and characterisation of benzyl phosphino-thioether and -thiolato Pd(II) complexes and their applications in Suzuki coupling reactions

Synthesis and characterisation of benzyl phosphino-thioether and -thiolato Pd(II) complexes and their applications in Suzuki coupling reactions
Synthesis and characterisation of benzyl phosphino-thioether and -thiolato Pd(II) complexes and their applications in Suzuki coupling reactions
The synthesis of the benzyl phosphinothioether derivatives Ph2PCH2CH(Et)SR and their corresponding palladium complexes are reported, where R = CH2Ph (3), R = CH2Ph (3), R = CH2-3,5-Me-C6H3 (4) and R = 1-CH2C10H7 (5). Crystallographic data obtained for the complexes Pd(3)Cl-2 and Pd(4)Cl-2 show intra- and inter-molecular pi-pi interactions between the aromatic rings on the P and S substituents, and NOE experiments for Pd(4)Cl-2 show that these interactions persist in solution. The performance of the phosphinothioether palladium complexes in aryl-aryl cross-coupling reactions is compared with that of the corresponding complex of the parent phosphinothiolato ligand Ph2PCH2CH(Et)S- (1). High turnover numbers up to 2000000 are reported for the coupling of bromobenzene, using the palladium dimer [Pd(1)I](2) as the catalyst precursor. Kinetic studies show a linear dependence of the reaction on catalyst loading. The effect of other variables on the cross-coupling reaction, such as temperature, solvent and base, is also reported.
high-activity catalysts, mixed phosphorus/sulfur ligands, x-ray structure, aryl chlorides, coordination chemistry, heck reaction, palladium(ii) complexes, allylic alkylation, enantioselective hydrogenation, asymmetric hydrogenation
1477-9226
5717-5724
Dervisi, Athanasia
967db740-d11c-43a5-af7d-75a9eb5ad162
Koursarou, Despina
3f563781-bcfe-4daf-8264-de83b529bb27
Ooi, Li-ling
7c5b6dd6-59d6-4036-8d06-3746602ca1cb
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Dervisi, Athanasia
967db740-d11c-43a5-af7d-75a9eb5ad162
Koursarou, Despina
3f563781-bcfe-4daf-8264-de83b529bb27
Ooi, Li-ling
7c5b6dd6-59d6-4036-8d06-3746602ca1cb
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Dervisi, Athanasia, Koursarou, Despina, Ooi, Li-ling, Horton, Peter N. and Hursthouse, Michael B. (2006) Synthesis and characterisation of benzyl phosphino-thioether and -thiolato Pd(II) complexes and their applications in Suzuki coupling reactions. Dalton Transactions, (48), 5717-5724. (doi:10.1039/b609607g).

Record type: Article

Abstract

The synthesis of the benzyl phosphinothioether derivatives Ph2PCH2CH(Et)SR and their corresponding palladium complexes are reported, where R = CH2Ph (3), R = CH2Ph (3), R = CH2-3,5-Me-C6H3 (4) and R = 1-CH2C10H7 (5). Crystallographic data obtained for the complexes Pd(3)Cl-2 and Pd(4)Cl-2 show intra- and inter-molecular pi-pi interactions between the aromatic rings on the P and S substituents, and NOE experiments for Pd(4)Cl-2 show that these interactions persist in solution. The performance of the phosphinothioether palladium complexes in aryl-aryl cross-coupling reactions is compared with that of the corresponding complex of the parent phosphinothiolato ligand Ph2PCH2CH(Et)S- (1). High turnover numbers up to 2000000 are reported for the coupling of bromobenzene, using the palladium dimer [Pd(1)I](2) as the catalyst precursor. Kinetic studies show a linear dependence of the reaction on catalyst loading. The effect of other variables on the cross-coupling reaction, such as temperature, solvent and base, is also reported.

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More information

Published date: 2006
Keywords: high-activity catalysts, mixed phosphorus/sulfur ligands, x-ray structure, aryl chlorides, coordination chemistry, heck reaction, palladium(ii) complexes, allylic alkylation, enantioselective hydrogenation, asymmetric hydrogenation

Identifiers

Local EPrints ID: 44421
URI: http://eprints.soton.ac.uk/id/eprint/44421
ISSN: 1477-9226
PURE UUID: 0cbb5492-5f93-4517-b490-bd5c56494992
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016

Catalogue record

Date deposited: 01 Mar 2007
Last modified: 20 Jul 2019 01:08

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