†Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
‡ChemMatCARS, The University of Chicago, Argonne, Illinois 60439, United States.
J Am Chem Soc. 2015 May 27;137(20):6472-5. doi: 10.1021/jacs.5b03192. Epub 2015 May 15.
Halogen photoelimination reactions constitute the oxidative half-reaction of closed HX-splitting energy storage cycles. Here, we report high-yielding, endothermic Cl2 photoelimination chemistry from mononuclear Ni(III) complexes. On the basis of time-resolved spectroscopy and steady-state photocrystallography experiments, a mechanism involving ligand-assisted halogen elimination is proposed. Employing ancillary ligands to promote elimination offers a strategy to circumvent the inherently short-lived excited states of 3d metal complexes for the activation of thermodynamically challenging bonds.
卤素光解反应构成了闭合 HX 分解储能循环的氧化半反应。在这里，我们报告了单核 Ni(III)配合物中高产率的、吸热的 Cl2 光解化学。基于时间分辨光谱和稳态光结晶实验，提出了一种涉及配体辅助卤素消除的机制。利用辅助配体促进消除为 3d 金属配合物中固有寿命短的激发态的活化提供了一种策略，从而激活热力学上具有挑战性的键。
