Ni2‐Imido Bispincer Platforms: Cooperative Reactivity Enabled Through Substrate Addition Across a Ni2N Unit
- 1Department of Chemistry University of Texas Rio Grande Valley Brownsville Texas USA
- 2Department of Chemistry University of Kansas Lawrence Kansas USA
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.
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BibTeX
@article{santos2026ni2imido,
title = {{Ni2‐Imido Bispincer Platforms: Cooperative Reactivity Enabled Through Substrate Addition Across a Ni2N Unit}},
author = {David de los Santos and Kritika Gour and Manar M. Shoshani},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = jul,
doi = {10.1002/chem.71379},
url = {https://doi.org/10.1002/chem.71379},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Ni2‐Imido Bispincer Platforms: Cooperative Reactivity Enabled Through Substrate Addition Across a Ni2N Unit
AU - David de los Santos
AU - Kritika Gour
AU - Manar M. Shoshani
PY - 2026
DA - 2026/07/18
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71379
UR - https://doi.org/10.1002/chem.71379
AB - 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.
SN - 0947-6539
SN - 1521-3765
ER -