Thursday, 26 June 2025 11:00am – 12:00pm

This seminar will be delivered in Chemistry Lecture Theatre 4

Speaker: Dr. Terrance J. Hadlington

Host: Dr Alex Yuen

Title: Leveraging Chemistry at the Molecular p-Block – Transition Metal Interface

Abstract
The Renaissance in main group chemistry over recent decades has given us a huge depth in understanding the electronic characteristics of low-valent p-block species.^1,2 The importance of developing sustainable chemical technologies, in conjunction with the impressive reactive capacity of the abundant p-block elements in non-classical oxidation states, has firmly established this chemistry as a cornerstone in modern synthesis, albeit in a largely fundamental capacity. In taking such species from laboratory curiosities to utility, our research focuses on developing the Single-Centre Ambiphile ligand concept.³ This concept utilises the ambiphilic frontier orbitals of now well established low-valent group 13 and 14 species, incorporating these elements into chelating ligands and thus forming a bespoke family of non-innocent ligand systems. These have the capacity to bind a transition metal centre through a lone electron pair, whilst the same binding centre remains highly Lewis acidic (Fig. 1). This, in turn, promotes nucleophile binding at the ligand centre, even in complexes containing sub- 18-electron transition metal centres. This opens a new mechanistic pathway for accessing hitherto unknown bond activation processes, moving towards catalysis.

Utilizing Single-Centre Ambiphile ligands, we have shown that stable complexes of Fe⁰, Co⁰, and Ni⁰ are readily accessible, with each transition metal displaying a unique reactive capacity. This is also dependent on the ligand’s binding centre (e.g. Ge^II vs. Sn^II), giving a high degree of control over these reactive systems. This and subsequent chemistry of these complexes will be discussed, including site- selective nucleophile binding, Lewis super-acidity, reversible small-molecule activation, and (switchable) alkene functionalisation catalysis in Ga^I, Ge^II, and Sn^II systems.⁴

Figure 1. The Single-Centre Ambiphile concept.

References

1. (a) Hadlington, T. J., Soc. Rev., 2024, 53, 9738-9831; (b) Hadlington, T. J., Chem. Soc. Rev., 2024, 53, 9718-9737.
2. Power, P. P. Nature, 2010, 463, 171.
3. Keil, P. M., Szilvasi, T., and Hadlington, T. J. Chem. Sci., 2021, 12, 5582.
4. (a) Kalkuhl, T., Fernandez, I., and Hadlington T. J., Chem, 2024, 11, 102349; (b) Keil, P. M., and Hadlington, T. J. Angew. Chem. Int. Ed. 2022, 134, e202114143; (c) Keil, P. M., and Hadlington, T. J. Chem. Commun. 2022, 58, 3011; (d) Keil, P. M., Soyemi, A., Weisser, K., Szilvási, S., Limberg, C., and Hadlington, T. J. Angew. Chem. Int. Ed. 2023, e202218141 ; (e) Schulz, A., Kalkuhl, T. L., Keil, P. M., and Hadlington, T. J., Angew. Chem. Int. Ed. 2023, e202305996.

Bio
Terry grew up in the UK, and received his MChem degree from the University of Bath in 2011. He then moved to Melbourne, Australia, where he conducted his PhD research with Prof. Cameron Jones at Monash University, utilizing heavier tetrylenes in catalysis and exploring low-valent group 14 chemistry more broadly. During this time, he also spent four months at the University of Oxford, working with Prof. Simon Aldridge. He then relocated to Berlin as a UniCat Postdoctoral Fellow with Prof. Matthias Driess. In late 2019, Terry started his independent research career at the TU Munich, supported by a Liebig Fellowship of the FCI. Here his fascination regarding the synergistic reactivity between low-valent main group ligands, such as gallylenes and stannylenes, and low-valent first row transition metals is a major topic of research. His team additionally develops chelating poly-phosphinidene ligands, and as well as investigating unexplored hydride chemistry of the alkaline earth metals, including beryllium.

Since establishing his independent research group in Munich, Terry has been awarded the Liebig Stipendium of the FCI (2019), two Independent Research grants from the DFG (2021, 2023), an Exploration Grant of the Boehringer Ingelheim Foundation (2022), as well as an ERC Starting Grant (2022). He was also the recipient of the 2022 Wöhler-BASF-Nachwuchs Preis of the GDCh, and the 2023 ADUC Preis.