School of Integrative Biological & Chemical Sciences Faculty Publications

Document Type

Article

Publication Date

7-18-2026

Abstract

Transition metal imido complexes are renowned for their capacity to undertake challenging 1,2 additions owing to the high basicity of the imido moiety. Access to transition metal imidos is often limited to the addition of organic azides to metal precursors, hindering the design of molecular constructs incorporating imido units. Bimetallic bispincer complexes, 1 and 2, are presented, which are anchored by a central imido moiety supported by pyridyl imine donors, forming highly planarized Ni2N-aryl cores. Complex 2, which also features a Ni─Ni σ-bond, is able to engage in cooperative substrate cleavage of main group hydrides via a formal 1,2 addition to generate paramagnetic Ni2–amido–hydrido complexes 3-BPin and 3-SiPh2H. The 1,2 addition products feature a geometric distortion from the planar core noted in 2, resulting in the destabilization of the Ni─Ni bond to generate a formally S = 1 state. The complexes have been characterized through x-ray diffraction, spectroscopic studies, and DFT calculations. Catalytic hydrofunctionalization with 2 and 3-BPin support of the 1,2 addition is an on-cycle process in catalysis.

Comments

Student publication.

© 2026 The Author(s). Chemistry – A European Journal published by Wiley-VCH GmbH.

This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

Publication Title

Chemistry–A European Journal

DOI

10.1002/chem.71379

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