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Published May 27, 2015 | Version Supplemental Material
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Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes

Creators

  • 1. ROR icon Harvard University
  • 2. ROR icon University of Chicago

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.

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Supplemental Material - ja5b03192_si_001.pdf

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Additional details

Identifiers

Eprint ID
87025
DOI
10.1021/jacs.5b03192
Resolver ID
CaltechAUTHORS:20180612-143806306

Related works

Describes
10.1021/jacs.5b03192 (DOI)

Funding

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

Dates

Created
2018-06-12
Created from EPrint's datestamp field
Updated
2021-11-15
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