Photohalogen elimination chemistry in low-valent binuclear nickel complexes

Creators: Jun Hwang, Seung; Hadt, Ryan G.; Ruccolo, Serge; Gygi, David; Zheng, Shao-Liang; Chen, Yu-Sheng; Nocera, Daniel G.

Abstract

The photogeneration of X₂ is the key to achieving an efficient HX-splitting photocycle, as it is more thermodynamically and kinetically challenging than its H₂ half reaction counterpart. Here we report a strategy that enables Cl₂ photoelimination from low-valent binuclear d⁹–d⁹ and d⁹–d¹⁰ Ni complexes. We demonstrate the importance a of metal–metal bond interaction for M–X bond photoactivation with a combination of TD-DFT computations together with spectroscopy and photocrystallography, exemplifying a design principle for future developments of 3d metal complexes for HX photocatalysis.

Additional Information

© 2021 Elsevier Ltd. Received 6 March 2021, Revised 11 April 2021, Accepted 13 April 2021, Available online 18 April 2021. This work was supported by the National Science Foundation under grant CHE-1855531. RGH acknowledges support from the ANL Enrico Fermi Fellowship. DG acknowledges the National Science Foundation (NSF) for a Graduate Research Fellowship Program (GRFP). We thank James Lawniczak for help with ligand preparations. Photocrystallography was carried out at ChemMatCARS, Sector 15, APS, which is principally supported by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant number NSF/CHE-1346572. Use of the PILATUS3 X CdTe 1 M detector is supported by the National Science Foundation under the grant number NSF/DMR-1531283. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. We gratefully acknowledge the computing resources provided on Blues, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory (ANL). We present this work in recognition of the accomplishments and penetrating contributions by Professor Malcolm Green to our understanding of organometallic chemistry and synthetic materials science. The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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