Perez-Jimenez Marina, Geoghegan Blaise L, Collauto Alberto, Röβler Maxie M, Crimmin Mark R
Department of Chemistry and Centre for Pulse EPR spectroscopy (PEPR), Imperial College London, 82 Wood Lane, Shepherds Bush, London, W12 0BZ, UK.
Angew Chem Int Ed Engl. 2024 Nov 18;63(47):e202411828. doi: 10.1002/anie.202411828. Epub 2024 Oct 14.
Reaction of a molecular zinc-hydride [{(ArNCMe)CH}ZnH] (Ar=2,6-di-isopropylphenyl) with 0.5 equiv. of [Ni(CO)Cp] 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 D or dehydrocoupling to form Zn-Zn bonds. In combination, the data support the activation and functionalisation of zinc-hydride bonds at nickel(I) centres.
分子氢化锌[{(ArNCMe)CH}ZnH]（Ar = 2,6 - 二异丙基苯基）与0.5当量的[Ni(CO)Cp]反应，得到了一种含有桥连三中心、两电子Ni - H - Zn相互作用的镍 - 锌氢化物配合物。该物种已通过单晶X射线衍射在固态下进行了表征。密度泛函理论计算结果与它作为由氢化锌与顺磁性镍（I）片段配位衍生而来的σ - 配合物的结构相符。连续波和脉冲电子顺磁共振实验表明，该物种在溶液中不稳定。进一步的实验表明，在催化量的镍（I）前体存在下，氢化锌键可与D进行H/D交换或发生脱氢偶联形成Zn - Zn键。综合来看，这些数据支持了镍（I）中心对氢化锌键的活化和官能化作用。
