Issue 28, 2022

Engendering reactivity at group 5-heteroatom multiple bonds via π-loading

Abstract

In this Perspective, we discuss the strategy of π-loading, i.e., coordination of two or more strongly π-donating ligands to a single metal center, as it applies to promoting reactivity at group 5 transition metal-imido groups. When multiple π-donor ligands compete to interact with the same symmetrically-available metal dπ orbitals, the energy of the imido-based frontier molecular orbitals increases, leading to amplified imido-based reactivity. This strategy is of particular relevance to group 5 metals, as mono(imido) complexes of these metals tend to be inert at the imido group. Electronic structure studies of group 5 bis(imido) complexes are presented, and examples of catalytically and stoichiometrically active group 5 bis(imido) and chalcogenido–imido complexes are reviewed. These examples are intended to encourage future work exploring π-loaded bis(imido) systems of the group 5 triad.

Graphical abstract: Engendering reactivity at group 5-heteroatom multiple bonds via π-loading

Article information

Article type
Perspective
Submitted
14 5 2022
Accepted
20 6 2022
First published
29 6 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 8224-8242

Engendering reactivity at group 5-heteroatom multiple bonds via π-loading

J. I. Fostvedt, J. Mendoza, S. Lopez-Flores, D. Alcantar, R. G. Bergman and J. Arnold, Chem. Sci., 2022, 13, 8224 DOI: 10.1039/D2SC02706B

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