Boonseng, Sarote, Roffe, Gavin W, Targema, Msugh, Spencer, John and Cox, Hazel (2017) Rationalization of the mechanism of in situ Pd(0) formation for cross-coupling reactions from novel unsymmetrical pincer palladacycles using DFT calculations. Journal of Organometallic Chemistry, 845. pp. 71-81. ISSN 0022-328X

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Abstract

Density functional theory (DFT) is used to determine the mechanism for Pd(0) generation from pincer palladacycle pre-catalysts. The elucidated mechanisms comprise two key steps, transmetallation and reductive elimination. It is found that the presence of a base in the pre-catalyst activation step serves to significantly lower the Gibbs free energy barrier of the transmetallation step and the Gibbs free energy of the overall pre-catalyst activation. The DFT results are used to rationalize the catalytic activity of a number of pincer palladacycles in the Suzuki-Miyaura coupling of sterically demanding and electronically deactivated aryl bromides with 2-tolyboronic acid. A strong correlation exists between the Gibbs free energy barrier of the transmetallation step and/or overall pre-catalyst activation energy and the percentage conversions of the Suzuki- Miyaura coupling in the presence of the novel pre-catalysts. The data presented suggest that the slow, controlled release of the “true, active catalyst,” Pd(0), from the pincer palladacycle pre-catalysts provides the optimum reaction conditions and may be achieved by a high transmetallation energy barrier or overall pre-catalyst activation energy or both.

Item Type:	Article
Schools and Departments:	School of Life Sciences > Chemistry
Subjects:	Q Science > QD Chemistry > QD0146 Inorganic chemistry Q Science > QD Chemistry > QD0241 Organic chemistry
Depositing User:	John Spencer
Date Deposited:	13 Mar 2017 10:06
Last Modified:	01 Mar 2018 02:00
URI:	http://srodev.sussex.ac.uk/id/eprint/67061

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