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Updated: Jun 18, 2025

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
A Paramagnetic Nickel-Zinc Hydride Complex
Marina Perez-Jimenez1, Blaise L Geoghegan1, Alberto Collauto1
1Department of Chemistry and Centre for Pulse EPR spectroscopy (PEPR), Imperial College London, 82 Wood Lane, Shepherds Bush, London, W12 0BZ, UK.
Abstract:
Reaction of a molecular zinc-hydride [{(ArNCMe)2CH}ZnH] (Ar=2,6-di-isopropylphenyl) with 0.5 equiv. of [Ni(CO)Cp]2 led to the isolation of a nickel-zinc hydride complex containing a bridging 3-centre,2-electron Ni-H-Zn interaction. This species has been characterized in the solid-state by single crystal X-ray diffraction. DFT calculations are consistent with its formulation as a σ-complex derived from coordination of the zinc-hydride to a paramagnetic nickel(I) fragment. Continuous-wave and pulse EPR experiments suggest that this species is labile in solution. Further experiments show that in the presence of catalytic quantities of nickel(I) precursors, zinc-hydride bonds can undergo either H/D-exchange with D2 or dehydrocoupling to form Zn-Zn bonds. In combination, the data support the activation and functionalisation of zinc-hydride bonds at nickel(I) centres.
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