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 Mai 2022
Accepted
20 Jun 2022
First published
29 Jun 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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