@article{6c5451e76bdf441da60dfad75d1f3b47,
title = "Photosensitized activation of diazonium derivatives for C–B bond formation",
abstract = "Aryl diazonium salts are ubiquitous building blocks in chemistry, as they are useful radical precursors in organic synthesis as well as for the functionalization of solid materials. They can be reduced electrochemically or through a photo-induced electron transfer reaction. Here, we provide a detailed picture of the ground- and excited-state reactivity of a series of nine rare and earth-abundant photosensitizers with 13 aryl diazonium salts, which also included three macrocyclic calix[4]arene tetradiazonium salts. Nanosecond transient absorption spectroscopy confirmed the occurrence of excited-state electron transfer and was used to quantify cage-escape yields (i.e., the efficiency with which the formed radicals separate and escape the solvent cage). Cage-escape yields were large; they increased when the driving force for photo-induced electron transfer increased and also tracked with the C–N2+ bond cleavage propensity, among others. A photo-induced borylation reaction was then investigated with all the photosensitizers and proceeded with yields between 9% and 74%.",
keywords = "cage escape, catalysis, diazonium, electron transfer, Hammett, mechanism, photo-induced, photoredox, SDG3: Good health and well-being, transient",
author = "Alexia Ripak and {De Kreijger}, Simon and Sampaio, {Renato N.} and Vincent, {Cooper A.} and {\'E}milie Cau{\"e}t and Ivan Jabin and Tambar, {Uttam K.} and Benjamin Elias and Ludovic Troian-Gautier",
note = "Funding Information: Financial support was provided to A.R. by the F.R.S.- FNRS (FRIA fellowship). This work was supported by the Fonds de la Recherche Scientifique (F.R.S.-FNRS) under grant no. U.N021.21 (B.E.). L.T.-G. is a Chercheur Qualifi{\'e} of the Fonds de la Recherche Scientifique -FNRS. S.D.K., B.E., and L.T.-G. gratefully acknowledge the UCLouvain for financial support. Computational resources have been provided by the Consortium des {\'E}quipements de Calcul Intensif (C{\'E}CI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under grant no. 2.5020.11 and by the Walloon Region . Financial support was provided to U.K.T. by W.W. Caruth , Jr. Endowed Scholarship , Welch Foundation ( I-1748 ), National Institutes of Health ( R01GM102604 ), American Chemical Society Petroleum Research Fund ( 59177-ND1 ), and Teva Pharmaceuticals Marc A. Goshko Memorial Grant ( 60011-TEV ). Financial support was provided to C.A.V. by Sarah and Frank McKnight Fund Graduate Fellowship. Funding Information: Financial support was provided to A.R. by the F.R.S.-FNRS (FRIA fellowship). This work was supported by the Fonds de la Recherche Scientifique (F.R.S.-FNRS) under grant no. U.N021.21 (B.E.). L.T.-G. is a Chercheur Qualifi{\'e} of the Fonds de la Recherche Scientifique-FNRS. S.D.K. B.E. and L.T.-G. gratefully acknowledge the UCLouvain for financial support. Computational resources have been provided by the Consortium des {\'E}quipements de Calcul Intensif (C{\'E}CI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under grant no. 2.5020.11 and by the Walloon Region. Financial support was provided to U.K.T. by W.W. Caruth, Jr. Endowed Scholarship, Welch Foundation (I-1748), National Institutes of Health (R01GM102604), American Chemical Society Petroleum Research Fund (59177-ND1), and Teva Pharmaceuticals Marc A. Goshko Memorial Grant (60011-TEV). Financial support was provided to C.A.V. by Sarah and Frank McKnight Fund Graduate Fellowship. A.R. and S.D.K. conducted the experiments. C.A.V. performed initial photoreactions using [Ru(bpy)3]2+ and MeO-benzene diazonium. E.C. designed and performed computational experiments. R.N.S. performed the kinetic modeling for the dark state reactivity. I.J. provided the calix[4]arene derivatives. L.T.-G. B.E. and U.K.T. conceptualized, designed the experiments, and supervised the research. All the authors analyzed and interpreted the data and wrote and edited the manuscript. The authors declare no competing interests. We support inclusive, diverse, and equitable conduct of research. Publisher Copyright: {\textcopyright} 2022 Elsevier Inc.",
year = "2023",
month = feb,
day = "16",
doi = "10.1016/j.checat.2022.100490",
language = "English (US)",
volume = "3",
journal = "Chem Catalysis",
issn = "2667-1107",
publisher = "Cell Press",
number = "2",
}