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

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posted on 2023-06-09, 00:48 authored by Gavin W Roffe, Sarote Boonseng, Christine B Baltus, Simon J Coles, Iain Day, Rhiannon N Jones, Neil J Press, Mario Ruiz, Graham J Tizzard, Hazel CoxHazel Cox, John SpencerJohn Spencer
The SCN ligand 2-{3 [(methylsulfanyl)methyl]phenyl}pyridine, 1, has been synthesized starting froman 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.

History

Publication status

  • Published

File Version

  • Published version

Journal

Royal Society Open Science

ISSN

2054-5703

Publisher

Royal Society

Issue

4

Volume

3

Page range

150656

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2016-04-07

First Open Access (FOA) Date

2016-04-07

First Compliant Deposit (FCD) Date

2016-04-06

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