Determining structure and Zn-specific Lewis acid-base descriptors for diorganozincs in non-coordinating solvents using X-ray spectroscopy

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Parker, L. G. ORCID: https://orcid.org/0000-0001-8727-4116, Towers Tompkins, F. K., Seymour, J. M., Alblewi, N., Gousseva, E., Daw, M. R. ORCID: https://orcid.org/0000-0003-0043-7096, Hayama, S., Matthews, R. P. ORCID: https://orcid.org/0000-0003-3328-4954, Fouda, A. E. A. ORCID: https://orcid.org/0000-0002-9445-5537, Elliott, J. D., Smith, C. D. ORCID: https://orcid.org/0000-0002-5911-5836 and Lovelock, K. R. J. ORCID: https://orcid.org/0000-0003-1431-269X (2025) Determining structure and Zn-specific Lewis acid-base descriptors for diorganozincs in non-coordinating solvents using X-ray spectroscopy. Communications Chemistry, 8. 294. ISSN 2399-3669 doi: 10.1038/s42004-025-01704-x

Abstract/Summary

Diorganozinc reagents (ZnR2, e.g. R = Et, Ph, C6F5) are widely used as Lewis acid catalysts or Lewis base reagents in their own right. However, descriptors for predicting the influence of the R substituent on ZnR2 Lewis acidity/basicity are very sparse. This is because ZnR2 liquid-phase speciation and electronic structure are unknown to date due to zinc’s ‘spectroscopically quiet’ nature and inability to measure ‘at zinc’. Here, we identify the geometric structures of ZnR2 in weakly coordinating solvents, demonstrating that electronic structure factors will dominate reactivity. We quantify the electronic structure properties that dictate ZnR2 Lewis acidity/basicity using three newly developed zinc-specific descriptors by combining the results from three zinc-specific X-ray spectroscopy methods and calculations. We provide accessible methods to pre-screen ZnR2 reactivity. Furthermore, our X-ray spectroscopy toolkit offers opportunities to develop liquid-phase descriptors that dictate reactivity for other zinc species, e.g. zinc bis-amides, battery electrolytes and enzymes.

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Item Type Article
URI https://centaur.reading.ac.uk/id/eprint/124882
Identification Number/DOI 10.1038/s42004-025-01704-x
Refereed Yes
Divisions Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > NMR (CAF)
Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > Optical Spectroscopy (CAF)
Uncontrolled Keywords Organometallic Chemistry Physical Chemistry Spectroscopy Synchrotron
Publisher Springer Nature
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