Issue 2, 2024

Ligand-enforced geometric constraints and associated reactivity in p-block compounds

Abstract

The geometry at an element centre can generally be predicted based on the number of electron pairs around it using valence shell electron pair repulsion (VSEPR) theory. Strategies to distort p-block compounds away from these predicted geometries have gained considerable interest due to the unique structural outcomes, spectroscopic properties or reactivity patterns engendered by such distortion. This review presents an up-to-date group-wise summary of this exciting and rapidly growing field with a focus on understanding how the ligand employed unlocks structural features, which in turn influences the associated reactivity. Relevant geometrically constrained compounds from groups 13–16 are discussed, along with selected stoichiometric and catalytic reactions. Several areas for advancement in this field are also discussed. Collectively, this review advances the notion of geometric tuning as an important lever, alongside electronic and steric tuning, in controlling bonding and reactivity at p-block centres.

Graphical abstract: Ligand-enforced geometric constraints and associated reactivity in p-block compounds

Article information

Article type
Review Article
Submitted
12 Leo 2023
First published
15 Tsh 2023

Chem. Soc. Rev., 2024,53, 764-792

Ligand-enforced geometric constraints and associated reactivity in p-block compounds

T. J. Hannah and S. S. Chitnis, Chem. Soc. Rev., 2024, 53, 764 DOI: 10.1039/D3CS00765K

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