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Data from: A synthetic, catalytic and theoretical investigation of an unsymmetrical SCN pincer palladacycle

Data from: A synthetic, catalytic and theoretical investigation of an unsymmetrical SCN pincer palladacycle
Data from: A synthetic, catalytic and theoretical investigation of an unsymmetrical SCN pincer palladacycle
The SCN ligand 2-{3-[(methylsulfanyl)methyl]phenyl}pyridine, 1, has been synthesized starting from an initial Suzuki–Miyaura (SM) coupling between 3-((hydroxymethyl)phenyl)boronic acid and 2-bromopyridine. The C–H activation of 1 with in situ formed Pd(MeCN)4(BF4)2 has been studied and leads to a mixture of palladacycles, which were characterized by X-ray crystallography. The monomeric palladacycle LPdCl 6, where L-H = 1, has been synthesized, and tested in SM couplings of aryl bromides, where it showed moderate activity. Density functional theory and the atoms in molecules (AIM) method have been used to investigate the formation and bonding of 6, revealing a difference in the nature of the Pd–S and Pd–N bonds. It was found that S-coordination to the metal in the rate determining C–H bond activation step leads to better stabilization of the Pd(II) centre (by 13–28 kJ mol−1) than with N-coordination. This is attributed to the electron donating ability of the donor atoms determined by Bader charges. The AIM analysis also revealed that the Pd–N bonds are stronger than the Pd–S bonds influencing the stability of key intermediates in the palladacycle formation reaction pathway.,Royal Society Open Science Supplementary info final version,
Dryad Digital Repository
Roffe, Gavin W.
77d00ee6-a56e-49ed-af4a-670b5c452ade
Boonseng, Sarote
83b6e024-fc9d-4f5f-9dc4-0e7c4c10d34f
Baltus, Christine B.
9345057c-8fc2-447d-aaf4-ee613ad4d131
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Day, Iain J.
63855d2b-1a0e-485e-b84f-9c1a6bca9a0e
Jones, Rhiannon N.
e0b86e49-17e9-4b7b-aa42-3d0e35aa0d32
Press, Neil J.
ee2e10f8-f371-4bf6-9c23-e385d0e16406
Ruiz, Mario
bd7598ee-5b4b-4052-9b2d-a5d5ac54d51c
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Cox, Hazel
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Spencer, John
a3cf55cd-a4c7-4af6-b16c-96c8fb8c4cf4
Roffe, Gavin W.
77d00ee6-a56e-49ed-af4a-670b5c452ade
Boonseng, Sarote
83b6e024-fc9d-4f5f-9dc4-0e7c4c10d34f
Baltus, Christine B.
9345057c-8fc2-447d-aaf4-ee613ad4d131
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Day, Iain J.
63855d2b-1a0e-485e-b84f-9c1a6bca9a0e
Jones, Rhiannon N.
e0b86e49-17e9-4b7b-aa42-3d0e35aa0d32
Press, Neil J.
ee2e10f8-f371-4bf6-9c23-e385d0e16406
Ruiz, Mario
bd7598ee-5b4b-4052-9b2d-a5d5ac54d51c
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Cox, Hazel
334ee45b-6c64-4c3b-a3e0-2a72f342f2cf
Spencer, John
a3cf55cd-a4c7-4af6-b16c-96c8fb8c4cf4

Roffe, Gavin W., Boonseng, Sarote, Baltus, Christine B., Day, Iain J., Press, Neil J., Ruiz, Mario, Cox, Hazel and Spencer, John (2016) Data from: A synthetic, catalytic and theoretical investigation of an unsymmetrical SCN pincer palladacycle. Dryad Digital Repository doi:10.5061/dryad.mh57b [Dataset]

Record type: Dataset

Abstract

The SCN ligand 2-{3-[(methylsulfanyl)methyl]phenyl}pyridine, 1, has been synthesized starting from an initial Suzuki–Miyaura (SM) coupling between 3-((hydroxymethyl)phenyl)boronic acid and 2-bromopyridine. The C–H activation of 1 with in situ formed Pd(MeCN)4(BF4)2 has been studied and leads to a mixture of palladacycles, which were characterized by X-ray crystallography. The monomeric palladacycle LPdCl 6, where L-H = 1, has been synthesized, and tested in SM couplings of aryl bromides, where it showed moderate activity. Density functional theory and the atoms in molecules (AIM) method have been used to investigate the formation and bonding of 6, revealing a difference in the nature of the Pd–S and Pd–N bonds. It was found that S-coordination to the metal in the rate determining C–H bond activation step leads to better stabilization of the Pd(II) centre (by 13–28 kJ mol−1) than with N-coordination. This is attributed to the electron donating ability of the donor atoms determined by Bader charges. The AIM analysis also revealed that the Pd–N bonds are stronger than the Pd–S bonds influencing the stability of key intermediates in the palladacycle formation reaction pathway.,Royal Society Open Science Supplementary info final version,

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Published date: 1 January 2016

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Local EPrints ID: 448584
URI: http://eprints.soton.ac.uk/id/eprint/448584
PURE UUID: 1813b4fd-9773-4c29-b7cb-779aaef8b5a4
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Graham J. Tizzard: ORCID iD orcid.org/0000-0002-1577-5779

Catalogue record

Date deposited: 27 Apr 2021 16:43
Last modified: 28 Apr 2021 01:37

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Contributors

Creator: Gavin W. Roffe
Creator: Sarote Boonseng
Creator: Christine B. Baltus
Contributor: Simon J. Coles ORCID iD
Creator: Iain J. Day
Contributor: Rhiannon N. Jones
Creator: Neil J. Press
Creator: Mario Ruiz
Contributor: Graham J. Tizzard ORCID iD
Creator: Hazel Cox
Creator: John Spencer

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