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

Journal of the American Chemical Society
Stephen I TingAbigail G Doyle

Abstract

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 wa...Continue Reading

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Citations

Sep 25, 2020·Chemical Communications : Chem Comm·Thomas Rigotti, José Alemán
Oct 29, 2020·Chemistry : a European Journal·Oliver S Wenger
Jan 30, 2021·Accounts of Chemical Research·Stavros K Kariofillis, Abigail G Doyle
Jan 20, 2021·Journal of the American Chemical Society·Yangzhong QinDaniel G Nocera
Mar 5, 2021·Journal of the American Chemical Society·Mark W CampbellGary A Molander
Nov 14, 2020·Angewandte Chemie·Gang LiDong Xue
Apr 13, 2021·Journal of the American Chemical Society·Aleksandr O LykhinLaura Gagliardi
Jun 3, 2021·Journal of the American Chemical Society·Bernard G StevensonJohn R Swierk
Jun 16, 2021·Journal of the American Chemical Society·Nicholas A TillMatthew J Bird
Jun 25, 2021·Chemical Science·Raphael LauensteinCorinna R Hess
Jun 15, 2021·Angewandte Chemie·Narayan SinhaOliver S Wenger
Jun 17, 2020·The Journal of Physical Chemistry Letters·Remi FayadFelix N Castellano
Oct 8, 2020·Journal of the American Chemical Society·Ya-Ming TianTodd B Marder
Nov 24, 2020·The Journal of Physical Chemistry. a·David A CaganRyan G Hadt
Jan 16, 2021·Journal of the American Chemical Society·Simon KaufholdPetter Persson
Jan 13, 2021·Journal of the American Chemical Society·Jakob B BilgerOliver S Wenger
Sep 17, 2021·Journal of the American Chemical Society·Akin AydoganLudovic Troian-Gautier
Oct 9, 2021·Chemical Reviews·Kelvin Pak Shing CheungVladimir Gevorgyan

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