Ni₂-Imido Bispincer Platforms: Cooperative Reactivity Enabled Through Substrate Addition Across a Ni₂N Unit

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.