Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes
2015; American Chemical Society; Volume: 137; Issue: 20 Linguagem: Inglês
10.1021/jacs.5b03192
ISSN1943-2984
AutoresSeung Jun Hwang, David C. Powers, Andrew G. Maher, Bryce L. Anderson, Ryan G. Hadt, Shao‐Liang Zheng, Yu‐Sheng Chen, Daniel G. Nocera,
Tópico(s)Organic and Molecular Conductors Research
ResumoHalogen 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.
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