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A Synthetic, Catalytic and Theoretical Investigation of an Unsymmetrical SCN Pincer Palladacycle

Roffe, Gavin, Boonseng, Sarote, Baltus, Christine, Coles, Simon, Day, Iain, Jones, Rhiannon, Press, Neil, 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). p. 150656. ISSN 2054-5703


The SCN ligand, 2-{3-[(methylsulfanyl)methyl]phenyl}pyridine, 1 has been synthesized starting from an initial Suzuki-Miyaura 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 Suzuki-Miyaura couplings of aryl bromides, where it showed moderate activity. DFT 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.

Item Type: Article
Date Deposited: 20 May 2016 23:45
Last Modified: 20 May 2016 23:45


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