Making and Breaking Chemical Bonds with Electron Rich Main Group Compounds

Jamie Hicks, Josef T. Boronski, Petra Vasko, Andreas Heilmann, Caitilin B. McManus, Debotra Sarkar & Simon Aldridge
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK; [email protected]

The activation and functionalization of chemical bonds are critical fundamental processes which underpin chemical synthesis. While such processes have been exploited in catalytic fashion primarily through the application of late transition (‘Noble’) metal catalysts, other approaches involving ‘base’ 3d metals, frustrated Lewis pairs and Main Group elements have recently begun to emerge.[1]
We have been interested in developing p-block compounds that possess ‘transition- metal-like’ attributes critical for the activation of small molecules: (i) small HOMO- LUMO gaps; (ii) high energy HOMOs for the activation of kinetically inert bonds; (iii) unpaired electrons; and/or (iv) redox properties appropriate for reversible bond formation. This work has led to the development of novel systems for the activation of industrially relevant small molecules such as dihydrogen, ammonia, carbon monoxide/dioxide and hydrocarbons such as benzene.[2-8]












[1] See, for example: P. P. Power, Nature, 2010, 463, 171.
[2] A. V. Protchenko, K. Birjkumar, D. Dange, A. Schwarz, D. Vidovic, C. Jones, N. Kaltsoyannis, P. Mountford, S. Aldridge, J. Am. Chem. Soc., 2012, 134, 6500.
[3] A. Rit, J. Campos, H. Niu, S. Aldridge, Nature Chem., 2016, 8, 1022.
[4] J. Hicks, P. Vasko, J. M. Goicoechea, S. Aldridge, Nature, 2018, 557, 92.
[5] J. Hicks, A. Mansikkamaki, P. Vasko, J. M. Goicoechea, S. Aldridge, Nature Chem., 2019, 11, 237.
[6] J. Hicks, A. Heilmann, P. Vasko, J. M. Goicoechea, S. Aldridge, Angew. Chem. Int. Ed., 2019, 58, 17265.
[7] A. Heilmann, J. Hicks, P. Vasko, J. M. Goicoechea, S. Aldridge, Angew. Chem. Int. Ed., 2020, 59, 4897.
[8] J. Hicks, P. Vasko, J. M. Goicoechea, S. Aldridge, J. Am. Chem. Soc., 2019, 141, 11000.