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

A synthetic, catalytic and theoretical investigation of an unsymmetrical SCN pincer palladacycle
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.
1-15
Roffe, Gavin W.
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Boonseng, Sarote
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Baltus, Christine B.
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Coles, Simon
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Day, Iain J.
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Jones, Rhiannon N.
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Press, Neil J.
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Ruiz, Mario
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Tizzard, Graham
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Cox, Hazel
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Spencer, John
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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
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Day, Iain J.
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Jones, Rhiannon N.
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Press, Neil J.
ee2e10f8-f371-4bf6-9c23-e385d0e16406
Ruiz, Mario
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Tizzard, Graham
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Cox, Hazel
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Spencer, John
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Roffe, Gavin W., Boonseng, Sarote, Baltus, Christine B., Coles, Simon, Day, Iain J., Jones, Rhiannon N., Press, Neil J., Ruiz, Mario, Tizzard, Graham, Cox, Hazel and Spencer, John (2016) A synthetic, catalytic and theoretical investigation of an unsymmetrical SCN pincer palladacycle. Royal Society Open Science, 3 (4), 1-15. (doi:10.1098/rsos.150656).

Record type: Article

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.

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Accepted/In Press date: 1 March 2016
e-pub ahead of print date: 6 April 2016
Published date: 6 April 2016
Organisations: Organic Chemistry: SCF

Identifiers

Local EPrints ID: 402104
URI: http://eprints.soton.ac.uk/id/eprint/402104
PURE UUID: 6be38c40-1734-4ff6-944d-316fa1c53685
ORCID for Simon Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Graham Tizzard: ORCID iD orcid.org/0000-0002-1577-5779

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Date deposited: 02 Nov 2016 11:52
Last modified: 16 Mar 2024 03:05

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Contributors

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

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