3d-d Excited States of Ni(II) Complexes Relevant to Photoredox Catalysis: Spectroscopic Identification and Mechanistic Implications

Ting, Stephen I.; Garakyaraghi, Sofia; Taliaferro, Chelsea M.; Shields, Benjamin J.; Scholes, Gregory D.; Castellano, Felix N.; Doyle, Abigail G.

doi:10.1021/jacs.0c00781

³d-d Excited States of Ni(II) Complexes Relevant to Photoredox Catalysis: Spectroscopic Identification and Mechanistic Implications

Journal Article · Mon Mar 09 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c00781· OSTI ID:1603766

^[1]; Garakyaraghi, Sofia ^[2]; Taliaferro, Chelsea M. ^[3]; Shields, Benjamin J. ^[2]; ^[2]; ^[2]; ^[2]

Princeton Univ., NJ (United States). Dept. of Chemistry; Princeton University
Princeton Univ., NJ (United States). Dept. of Chemistry
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States

Synthetic organic chemistry has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni(^t-Bubpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment experimentally using a series of related complexes. Ultrafast UV–Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is ³d-d rather than ³MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using ¹H NMR techniques, supporting that this ³d-d state is tetrahedral and accessible at ambient temperature. Through a combination of transient absorption and NMR studies, the ³d-d state was determined to lie ~0.5 eV (12 kcal/mol) above the ground state. Because the ³d-d state features a weak Ni–aryl bond, the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of which are supported experimentally. Thus, photoinduced Ni–aryl homolysis offers a novel mechanism of initiating catalysis by Ni(I).

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Center (United States). BioLEC; Energy Frontier Research Centers (EFRC) (United States). Bioinspired Light-Escalated Chemistry (BioLEC); Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0019370

OSTI ID:: 1603766

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 12 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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