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Photolytic activation of Ni(II)X2L explains how Ni-mediated cross coupling begins

Year: 2025
Type: article
Abstract: In this work we seek to understand the pre-catalytic initiation steps in a classic metallaphotoredox catalysis paring Ir(III) ((Ir[dF(CF$_{3}$)ppy]$_{2}$(dtbbpy))PF$_{6}$) and Ni(II) ((4,4'-dtbbpy)NiCl$_{2}$) in dimethoxyethane. We use a combination of transient X-ray and optical absorption spectroscopies to track both nuclear and electronic excited-state dynamics, revealing two steps. First, photoexcitation produces the expected intramolecular oxidation of the iridium center, Ir(III), to Ir(IV)(dtbbpy)$^{\bullet -}$ correlated to the Ir metal-to-ligand charge transfer state. Second, interaction with Ir(IV)(dtbbpy)$^{\bullet -}$ drives the tetrahedral Ni(II) starting material to an unexpected octahedral Ni(II) species. We conclude by proposing the identity of the octahedral Ni(II) and suggest both an electron and an energy transfer mechanism for producing it that are equally consistent with our observations.
DOI: 10.1038/s41467-025-60729-x
Authors: Max Kudisch, Reagan X. Hooper, Lakshmy K. Valloli, Justin D. Earley, Anna Zieleniewska, Jin Yu, Stephen DiLuzio, Rebecca W. Smaha, Hannah Sayre, Xiaoyi Zhang, Matthew J. Bird, Amy A. Cordones, Garry Rumbles, Obadiah G. Reid
Institutions: National Laboratory of the Rockies, SLAC National Accelerator Laboratory, Brookhaven National Laboratory, University of Colorado Boulder, Argonne National Laboratory, Advanced Photon Source, Northeastern University
Language: English
Field: Chemistry
Open Access status: gold
Estimated APC paid: $6,990
Funders: U.S. Department of Energy, Office of Science, Basic Energy Sciences, Argonne National Laboratory, National Renewable Energy Laboratory, SLAC National Accelerator Laboratory
Awards: G102163711, G107546177, G1141120041, G1229526393, G1286251239, G1313983767, G1486108657, G14908310, G1505794299, G1664757510, G171842289, G1723423531, G1847291448, G2101401529, G2192028116, G2196865685, G2287611682, G2371548206, G241279073, G2522871517, G262532246, G262962599, G2887060908, G303061748, G3075337988, G340565428, G357145406, G4235786860, G426311843, G4269941704, G440252240, G4484984665, G4785159920, G4908923434, G495301720, G498139845, G5106849484, G5387317844, G5570207115, G566293355, G5765906131, BIOINSPIRED LIGHT-ESCALATED CHEMISTRY (BIOLEC), G5910536577, G618388848, G6234447384, G628751139, G6420323319, G6550344761, G6796042841, G6848031779, G6918803902, G6965541988, G7021897321, G7083997402, G7283024673, G7313278570, G7368700025, G7463374569, BIOINSPIRED LIGHT-ESCALATED CHEMISTRY (BIOLEC), G7583137537, G7626931543, G834333836, G8382000481, G847654844, G911061179, G944719100, G969889393, G993149817
OpenAlex ID: W4411887060
FWCI: 4.162
Cites: 70
Cited by: 17
Related to: 10