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      Review and Theoretical Analysis of Fluorinated Radicals in Direct C Ar−H Functionalization of (Hetero)arenes

      1 , 1 , 2 , 1
      Angewandte Chemie
      Wiley

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          Abstract

          We highlight key contributions in the field of direct radical C Ar− H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into three categories according to the electronic properties of the substrates. Density functional theory computational analysis provides insights into the chemical reactivity of several fluorinated radicals through their electrophilicity and nucleophilicity parameters. Theoretical analysis of their reduction potentials also highlights the remarkable correlation between electrophilicity and oxidizing ability. It is also established that highly fluorinated radicals (e.g. ⋅OCF 3) are capable of engaging in single‐electron transfer (SET) processes rather than radical addition, which is in good agreement with experimental literature data. A reactivity scale, based on activation barrier of addition of these radicals to benzene is also elaborated using the high accuracy DLPNO‐(U)CCSD(T) method.

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          Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density

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            Density-functional thermochemistry. III. The role of exact exchange

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              Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy.

              Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 molecules representing (nearly) all elements-except lanthanides-in their common oxidation states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, density functional theory and correlated methods, for which we had chosen Møller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.
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                Author and article information

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                Journal
                Angewandte Chemie
                Angewandte Chemie
                Wiley
                0044-8249
                1521-3757
                April 15 2024
                February 14 2024
                April 15 2024
                : 136
                : 16
                Affiliations
                [1 ] Department für Chemie und Biochemie Universität Bern Freiestrasse 3 3012 Bern Switzerland
                [2 ] Department of Chemistry and Biochemistry University of California 90095 Los Angeles California United States
                Article
                10.1002/ange.202318377
                c3077744-0554-47ae-82a9-26bea1cd98e8
                © 2024

                http://creativecommons.org/licenses/by-nc/4.0/

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