Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes
Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes
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DOI：
10.1021/jacs.5b03192
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发表时间：
2015-05-27
影响因子：
15
通讯作者：
Nocera, Daniel G.
中科院分区：
文献类型：
--
作者：
Hwang, Seung Jun;Powers, David C.;Nocera, Daniel G.
卤素光消除反应构成封闭HX分裂能量存储循环的氧化半反应。在这里，我们报告高产，吸热Cl-2光消除化学单核镍（III）配合物。在时间分辨光谱和稳态光晶体学实验的基础上，提出了配体辅助卤素消除的机理。采用辅助配体来促进消除提供了一种策略，以规避固有的短寿命的激发态的三维金属络合物的激活的化学挑战性的债券。
Halogen photoelimination reactions constitute the oxidative half-reaction of closed HX-splitting energy storage cycles. Here, we report high-yielding, endothermic Cl-2 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.