120th General Meeting of the KCS

Type Poster Presentation
Area Inorganic Chemistry
Room No. Exhibition Hall 2+3
Time 10월 19일 (목요일) 11:00~12:30
Code INOR.P-26
Subject Theoretical Elucidation of Catalytic Borylation of Methane
Authors Seihwan Ahn, Daniel J. Mindiola1,*, Mu-Hyun Baik*
Department of Chemistry, Korea Advanced Institute of Science and Technology, Korea
1Department of Chemistry, University of Pennsylvania, Korea
Abstract The C–H functionalization of hydrocarbon using Ir catalyst has been studied so far.[1] In particular, C–H bond activation of methane is one of the intriguing challenges because of its stability and inertness. We are, therefore, interested in the catalyst design for methane activation. Recently, we reported the catalytic borylation of methane by combining computational and experimental study.[2] Experimentally, we obtained monoborylated methane with 2–5% yield with Ir(1,10-phenanthroline)(Bpin)3 (pin = pinacol) catalyst, whereas Ir(dmpe)(Bpin)3 catalyst generates with 52% yield.[2] Herein, we suggest a suitable mechanism and elucidate the catalytic difference of two catalysts using DFT calculations. The calculation results show that the overall barrier for the Ir(dmpe)(Bpin)3 is lower than that of Ir(1,10-phenanthroline)(Bpin)3, which is good agreement with the previous results. In addition, based on HSAB principle, we can explain the catalytic difference between two ligands. References [1] (a) Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507. (b) Bergman, R. G. Nature 2007, 446, 391. (c) Hartwig, J. F. Acc. Chem. Res. 2012, 45, 864. [2] Smith, K. T.; Berritt, S.; Gonzalez, M.; Ahn, S.; Smith, M. R. III.; Baik, M.-H.; Mindiola, D. J. Science 2016, 351, 1424.
E-mail seihwanahn@kaist.ac.kr