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C–H bond cleavage occurring on a Rh(V) intermediate: a theoretical study of Rh-catalyzed arene azidation

Abstract

The sequence of C–H bond cleavage, oxidation addition, and reductive elimination is often proposed to account for Rh(III)-catalyzed arene functionalization. Invariably, C–H bond cleavage is the rate-limit step. In our present work, the sequence of steps in Rh-catalyzed C–H azidation of arenes is theoretically studied by the density functional theory method M11-L. Theoretical calculations indicated that the oxidation of Rh(III) to Rh(V) by PhI(OAc)OTs is a facile process. Subsequent electrophilic deprotonation, which is the rate-determining step, was shown to occur from a Rh(V) intermediate rather than a Rh(III) intermediate. Finally, the C-N3 reductive elimination from a cyclometalated Rh(V) complex could give the azidation product and regenerate the Rh(III) catalyst. Moreover, natural population analysis (NPA) of the oxidation process clarified that Rh(III) is oxidized to Rh(V) by trivalent iodine.

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Publication details

The article was received on 21 Nov 2017, accepted on 02 Feb 2018 and first published on 05 Feb 2018


Article type: Paper
DOI: 10.1039/C7CY02367G
Citation: Catal. Sci. Technol., 2018, Accepted Manuscript
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    C–H bond cleavage occurring on a Rh(V) intermediate: a theoretical study of Rh-catalyzed arene azidation

    S. Liu, X. Qi, R. Bai and Y. Lan, Catal. Sci. Technol., 2018, Accepted Manuscript , DOI: 10.1039/C7CY02367G

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