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Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes

Hwang, Seung Jun and Powers, David C. and Maher, Andrew G. and Anderson, Bryce L. and Hadt, Ryan G. and Zheng, Shao-Liang and Chen, Yu-Sheng and Nocera, Daniel G. (2015) Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes. Journal of the American Chemical Society, 137 (20). pp. 6472-6475. ISSN 0002-7863. doi:10.1021/jacs.5b03192.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Hadt, Ryan G.0000-0001-6026-1358
Nocera, Daniel G.0000-0001-5055-320X
Additional Information:© 2015 American Chemical Society. Received: March 26, 2015. Published: May 7, 2015. We gratefully acknowledge the NSF for funding (CHE–1332783). D.C.P. is supported by a Ruth L. Kirchenstein National Research Service award (F32GM103211). Photocrystallography was carried out at ChemMatCARS, Sector 15, APS, which is principally supported by the NSF/DOE (NSF/CHE-1346572). Use of APS was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. We thank Prof. G. M. Whitesides for access to calorimetry instrumentation. The authors declare no competing financial interest.
Funding AgencyGrant Number
NIH Predoctoral FellowshipF32GM103211
Department of Energy (DOE)DE-AC02-06CH11357
Issue or Number:20
Record Number:CaltechAUTHORS:20180612-143806306
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Official Citation:Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes Seung Jun Hwang, David C. Powers, Andrew G. Maher, Bryce L. Anderson, Ryan G. Hadt, Shao-Liang Zheng, Yu-Sheng Chen, and Daniel G. Nocera Journal of the American Chemical Society 2015 137 (20), 6472-6475 DOI: 10.1021/jacs.5b03192
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87025
Deposited By: George Porter
Deposited On:12 Jun 2018 21:55
Last Modified:15 Nov 2021 20:44

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