Halogen Photoelimination from Monomeric Nickel(III) Complexes Enabled by the Secondary Coordination Sphere
Abstract
Endothermic halogen elimination reactions, in which molecular halogen photoproducts are generated in the absence of chemical traps, are rare. Inspired by the proclivity of mononuclear Ni(III) complexes to participate in challenging bond-forming reactions in organometallic chemistry, we targeted Ni(III) trihalide complexes as platforms to explore halogen photoelimination. A suite of Ni(III) trihalide complexes supported by bidentate phosphine ligands has been synthesized and characterized. Multinuclear NMR, EPR, and electronic absorption spectroscopies, as well as single-crystal X-ray diffraction, have been utilized to characterize this suite of complexes as distorted square pyramidal, S = 1/2 mononuclear Ni(III) complexes. All complexes participate in clean halogen photoelimination in solution and in the solid state. Evolved halogen has been characterized by mass spectrometry and quantified chemically. Energy storage via halogen elimination was established by solution-phase calorimetry measurements; in all cases, halogen elimination is substantially endothermic. Time-resolved photochemical experiments have revealed a relatively long-lived photointermediate, which we assign to be a Ni(II) complex in which the photoextruded chlorine radical interacts with a ligand-based aryl group. Computational studies suggest that the observed intermediate arises from a dissociative LMCT excited state. The participation of secondary coordination sphere interactions to suppress back-reactions is an attractive design element in the development of energy-storing halogen photoelimination involving first-row transition metal complexes.
Additional Information
© 2015 American Chemical Society. Received: July 1, 2015; Published: September 4, 2015. Special Issue: Gregory Hillhouse Issue. We gratefully acknowledge the NSF for funding (CHE-1464232). D.C.P. is supported by a Ruth L. Kirchenstein National Research Service award (F32GM103211). Use of APS was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. We thank Prof. G. M. Whitesides for access to his laboratory's calorimetry instrumentation. In memory of our friend and colleague, Greg. Author Contributions: S. J. Hwang and B. L. Anderson contributed equally to this work. The authors declare no competing financial interest.Attached Files
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Supplemental Material - om5b00568_si_004.cif
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Additional details
- Eprint ID
- 86985
- DOI
- 10.1021/acs.organomet.5b00568
- Resolver ID
- CaltechAUTHORS:20180612-080212389
- CHE-1464232
- NSF
- F32GM103211
- NIH Predoctoral Fellowship
- DE-AC02-06CH11357
- Department of Energy (DOE)
- Created
-
2018-06-12Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field