Published May 27, 2015
| Supplemental Material
Journal Article
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Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes
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.
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.Attached Files
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Additional details
- Eprint ID
- 87025
- DOI
- 10.1021/jacs.5b03192
- Resolver ID
- CaltechAUTHORS:20180612-143806306
- CHE-1332783
- NSF
- F32GM103211
- NIH Predoctoral Fellowship
- CHE-1346572
- NSF
- DE-AC02-06CH11357
- Department of Energy (DOE)
- Created
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2018-06-12Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field