Stoichiometric and Catalytic Reactions of Thermally Stable Nickel(0) NHC Complexes
作者:Jianguo Wu、John W. Faller、Nilay Hazari、Timothy J. Schmeier
DOI:10.1021/om300045t
日期:2012.2.13
there are many organic reactions that are catalyzed by either Ni0 or Pd0 complexes, in comparison with the case for Pd0 there has been significantly less work studying coordinatively unsaturated Ni0 complexes. Here, we develop a simple synthetic route for preparing a number of thermally stable NHC-supported Ni0 hexadiene complexes in good yield. We examine the stoichiometric reactivity of one of these
Photochemical H<sub>2</sub> Evolution from Bis(diphosphine)nickel Hydrides Enables Low-Overpotential Electrocatalysis
作者:Bethany M. Stratakes、Kaylee A. Wells、Daniel A. Kurtz、Felix N. Castellano、Alexander J. M. Miller
DOI:10.1021/jacs.1c10628
日期:2021.12.22
mechanism of H2 evolution involving a short-lived singlet excited state that undergoes homolysis of the Ni–H bond. Thermodynamic analyses provide a basis for understanding and predicting the observed photoelectrocatalytic H2 evolution by a 3d transitionmetal based catalyst. Of particular note is the dramatic change in the electrochemical overpotential: in the dark, the nickel complexes require strong
既能收集光又能形成新化学键的分子有望用于太阳能燃料的生产,但缺乏这种第一行过渡金属光电催化剂。在这里,我们报告了用于 H 2析出的镍光电催化剂,利用可见光驱动的光化学 H 2从双(二膦)镍氢化物络合物中析出。一系列实验和理论分析,包括时间分辨光谱学和连续辐照量子产率测量,提出了一种 H 2演化机制,该机制涉及经历 Ni-H 键均裂的短寿命单重激发态。热力学分析为理解和预测观察到的光电催化 H 提供了基础2由 3d 过渡金属基催化剂演变而来。特别值得注意的是电化学过电位的显着变化:在黑暗中,镍络合物需要强酸,因此电催化需要高过电位;但在光照下,在相同施加电位下使用较弱的酸会导致电化学过电位提高 500 mV 以上。因此,对第一行过渡金属氢化物光化学的新见解能够在没有电化学过电位(在热力学电位或 0 mV 过电位下)的情况下实现光电催化 H 2演化。该催化剂系统不需要牺牲化学还原剂或光捕获半导体材料并产生