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Photohalogen elimination chemistry in low-valent binuclear nickel complexes

Jun Hwang, Seung and Hadt, Ryan G. and Ruccolo, Serge and Gygi, David and Zheng, Shao-Liang and Chen, Yu-Sheng and Nocera, Daniel G. (2021) Photohalogen elimination chemistry in low-valent binuclear nickel complexes. Polyhedron, 203 . Art. No. 115228. ISSN 0277-5387. doi:10.1016/j.poly.2021.115228.

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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.

Item Type:Article
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Hadt, Ryan G.0000-0001-6026-1358
Nocera, Daniel G.0000-0001-5055-320X
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.
Funding AgencyGrant Number
Argonne National LaboratoryUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
Department of Energy (DOE)DE-AC02-06CH11357
Subject Keywords:Solar; Photoactivation; Metal-chloride; Metal–metal; Hydrohalic acid splitting; Photocrystallography
Record Number:CaltechAUTHORS:20210423-082824488
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Official Citation:Seung Jun Hwang, Ryan G. Hadt, Serge Ruccolo, David Gygi, Shao-Liang Zheng, Yu-Sheng Chen, Daniel G. Nocera, Photohalogen elimination chemistry in low-valent binuclear nickel complexes, Polyhedron, Volume 203, 2021, 115228, ISSN 0277-5387, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108808
Deposited By: Tony Diaz
Deposited On:23 Apr 2021 16:04
Last Modified:05 May 2021 21:43

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