Mechanistic Insights into C-H Borylation of Arenes with Organoiridium Catalysts Embedded in a Microporous Metal-Organic Framework

Zoha H. Syed, Zhihengyu Chen, Karam B. Idrees, Timothy A. Goetjen, Evan C. Wegener, Xuan Zhang, Karena W. Chapman, David M. Kaphan*, Massimiliano Delferro, Omar K. Farha

*Corresponding author for this work

Research output: Contribution to journalArticle

2 Scopus citations

Abstract

Organometallic iridium catalysts can be used in conjunction with bispinacolatodiboron (B2Pin2) to effect the borylation of a variety of substrates such as arenes, alkanes, heteroarenes, and oxygenates. Recently, efforts have also focused on integrating these catalysts into porous supports, such as metal-organic frameworks (MOFs). While the mechanism of homogeneous borylation systems has been thoroughly investigated experimentally and computationally, analogous studies in MOF-supported iridium catalysts have not been conducted. Herein, we report the mechanistic investigation of a phenanthroline-iridium catalyst immobilized in the organic linker of Universitetet i Oslo (UiO)-67 (Zr6O4(OH)4(BPDC)4(PhenDC)2, BPDC = biphenyl-4,4′-dicarboxylate, PhenDC = 1,10-phenanthroline-4,4′-dicarboxylate). By using benzene as a model substrate, variable time normalization analysis (VTNA) of the kinetic data suggested a rate law consistent with zero-order in B2Pin2, and first-order in arene. A primary kinetic isotope effect (KIE) in the time course of benzene-d6 borylation also provided complementary information about the role of the arene in the rate-determining step of the reaction. Characterization by techniques such as X-ray absorption spectroscopy (XAS) confirmed the presence of Ir(III), while pair distribution function (PDF) analysis suggested structures containing an Ir-Cl bond, further substantiated by X-ray photoelectron spectroscopy (XPS). Analysis of postcatalysis materials by inductively coupled plasma-optical emission spectroscopy (ICP-OES) revealed low boron accumulation, which may indicate an absence of boron in the resting state of the catalyst. Finally, in comparing borylation of benzene and toluene, a slight selectivity for benzene is observed, which is similar to the analogous homogeneous reaction, indicating the influence of substrate sterics on reactivity.

Original languageEnglish (US)
Pages (from-to)1123-1133
Number of pages11
JournalOrganometallics
Volume39
Issue number7
DOIs
StatePublished - Apr 13 2020

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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    Syed, Z. H., Chen, Z., Idrees, K. B., Goetjen, T. A., Wegener, E. C., Zhang, X., Chapman, K. W., Kaphan, D. M., Delferro, M., & Farha, O. K. (2020). Mechanistic Insights into C-H Borylation of Arenes with Organoiridium Catalysts Embedded in a Microporous Metal-Organic Framework. Organometallics, 39(7), 1123-1133. https://doi.org/10.1021/acs.organomet.9b00874