Experimental and Theoretical Evidence for Relativistic Catalytic Activity in C-H Activation of N-Phenylbenzamide Using a Cationic Iridium Complex

Chinami Takashima, Hisaki Kurita, Hideaki Takano, Yasuhiro Ikabata, Takanori Shibata, Hiromi Nakai*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

This study elucidates that relativistic effect plays a key role in catalytic C-H activation using a cationic Ir complex. Experiments show that the cationic Ir(I)-diphosphine catalyst can be used for the deuterium substitution of N-phenylbenzamide, whereas a cationic Rh(I)-diphosphine catalyst is scarcely effective. Density functional theory calculations, including the relativistic effect, demonstrate a large difference in the reaction energy diagrams for the C-H activation of N-phenylbenzamide between the cationic Ir and Rh catalysts. In particular, the relatively low reaction barrier and considerably stabilized product obtained for the Ir catalysts are rationalized by strong Ir-C and Ir-H interactions, which originate from the relativistic self-consistent d-orbital expansion of Ir.

Original languageEnglish
Pages (from-to)7627-7638
Number of pages12
JournalJournal of Physical Chemistry A
Volume126
Issue number42
DOIs
Publication statusPublished - 2022 Oct 27

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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