A Well-defined NHC-Ir(iii) Catalyst for the Silylation of Aromatic C-H Bonds: Substrate Survey and Mechanistic Insights

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2017 Sep 30

PMID 28959403

Citations 11

Authors

Laura Rubio-Perez

Manuel Iglesias

Julen Munarriz

Victor Polo

Vincenzo Passarelli

Jesus J Perez-Torrente

Luis A Oro

Affiliations

Soon will be listed here.

Abstract

A well-defined NHC-Ir(iii) catalyst, [Ir(H)(IPr)(py)][BF] (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene), that provides access to a wide range of aryl- and heteroaryl-silanes by intermolecular dehydrogenative C-H bond silylation has been prepared and fully characterized. The directed and non-directed functionalisation of C-H bonds has been accomplished successfully using an arene as the limiting reagent and a variety of hydrosilanes in excess, including EtSiH, PhMeSiH, PhMeSiH, PhSiH and (EtO)SiH. Examples that show unexpected selectivity patterns that stem from the presence of aromatic substituents in hydrosilanes are also presented. The selective bisarylation of bis(hydrosilane)s by directed or non-directed silylation of C-H bonds is also reported herein. Theoretical calculations at the DFT level shed light on the intermediate species in the catalytic cycle and the role played by the ligand system on the Ir(iii)/Ir(i) mechanism.

Citing Articles

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