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. https://resolver.caltech.edu/CaltechAUTHORS:20180612-143806306

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Abstract

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:

URL	URL Type	Description
https://doi.org/10.1021/jacs.5b03192	DOI	Article
https://pubs.acs.org/doi/suppl/10.1021/jacs.5b03192	Publisher	Supporting Information

ORCID:

Author	ORCID
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.

Funders:

Funding Agency	Grant Number
NSF	CHE-1332783
NIH Predoctoral Fellowship	F32GM103211
NSF	CHE-1346572
Department of Energy (DOE)	DE-AC02-06CH11357

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DOI:

10.1021/jacs.5b03192

Record Number:

CaltechAUTHORS:20180612-143806306

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20180612-143806306

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

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ID Code:

87025

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CaltechAUTHORS

Deposited By:

George Porter

Deposited On:

12 Jun 2018 21:55

Last Modified:

15 Nov 2021 20:44

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