Transition metal catalysis
Transition metal catalysis is of paramount importance to both industry and academia where selectivity, activity and stability are crucial parameters to control. By taking advantage of the metal d-orbitals, these catalysts can activate substrates and accelerate reactions by means of coordination, ligand substitution, insertion, elimination etc., leading to the cleavage or formation of H−H, C−H and C−C bonds. With special regard to molecular catalysts, their activity and selectivity can be tuned by modification of their ligands with the result that numerous such catalysts have been developed and used in diverse fields such as medicines, pharmaceuticals, petrochemicals and materials.
Within the transition metal catalysis theme, we are interested in not only the development of new, more sustainable and improved molecular catalysts, but also the fundamental steps that underpin their catalytic cycles. Challenges being addressed include the activation of inert C-H bonds and molecules (e.g. CO2), through to the use of non-precious metals to allow greener and more atom-economical processes.
Some notable areas of current interest are:
- C-H bond activation and functionalisation
- Small molecule oligomerization and polymerization
- Hydrogenation and dehydrogenation
- Bimetallic catalysts with cooperative and synergistic effects
- "Understanding metal synergy in heterodinuclear catalysts for CO2/epoxide copolymerisation", A. C. Deacy, A. F. R. Kilpatrick, A. Regoutz and C. K. Williams, Nat. Chem., 2020, 12, 372. DOI:10.1038/s41557-020-0450-3.
- "Ruthenium-catalyzed hydrogenation of CO2 as a route to carboxylic acid methyl esters for use as biofuels or fine chemicals", Z. Wang, Z. Zhao, Y. Li, Y. Zhong, Q. Zhang, Q. Liu, G. A. Solan, Y. Ma and W.-H. Sun, Chem. Sci., 2020, 11, 6766-6774. DOI:10.1039/D0SC02942D.
- "The importance of kinetic and thermodynamic control when assessing mechanisms of carboxylate-assisted C–H activation", R. A. Alharis, C. L. McMullin, D. L. Davies, K. Singh and S. A. Macgregor, J. Am. Chem. Soc., 2019, 141, 8896-8906. DOI:10.1021/jacs.9b02073.
- "Enantioselective and regioselective copper-catalyzed borocyanation of 1-aryl-1,3-butadienes", T. Jia, M. J. Smith, A. P. Pulis, G. J. P. Perry and D J. Procter, ACS Catal., 2019, 9, 6744-6750. DOI:10.1021/acscatal.9b01911.
- "Efficient acceptorless dehydrogenation of secondary alcohols to ketones mediated by a PNN-Ru(II) catalyst", Z. Wang, B. Pan, Q. Liu, E. L. Yue, G. A. Solan, Y. Ma and W.-H. Sun, Catal. Sci. Tech., 2017, 7, 1654-1661. DOI:10.1039/c7cy00342k.
- "Cooperative interplay between a flexible PNN-Ru(II) complex and a NaBH4 additive in the efficient catalytic hydrogenation of esters", Z. Wang, X. Chen, B. Liu, Q.-B. Liu, G. A. Solan, X. Yang and W.-H. Sun, Catal. Sci. Tech., 2017, 7, 1297-1304. DOI:10.1039/c6cy02413k.
- "The reductive activation of CO2 across a Ti═Ti double bond: synthetic, structural, and mechanistic studies", A. F. R. Kilpatrick, J. C. Green and F. G. N. Cloke, Organometallics, 2015, 34, 4816-4829. DOI:10.1021/acs.organomet.5b00315.