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Electrophilic Si-H Activation by Acetonitrilo Benzo[h]quinoline Iridacycles: Influence of Electronic Effects in Catalysis.

Authors :
Behzadi M
Gajendramurthy CM
Boucher M
Deraedt C
Cornaton Y
Karmazin L
Gruber N
Bertani P
Djukic JP
Source :
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2023 Aug 01; Vol. 29 (43), pp. e202300811. Date of Electronic Publication: 2023 Jun 26.
Publication Year :
2023

Abstract

The performance of six newly synthesized benzo[h]quinoline-derived acetonitrilo pentamethylcyclopentadienyl iridium(III) tetrakis(3,5-bis-trifluoromethylphenyl)borate salts bearing different substituents -X (-OMe, -H, -Cl, -Br, -NO <subscript>2</subscript> and -(NO <subscript>2</subscript> ) <subscript>2</subscript> ) on the heterochelating ligand were evaluated in the dehydro-O-silylation of benzyl alcohol and the monohydrosilylation of 4-methoxybenzonitrile by Et <subscript>3</subscript> SiH, two reactions involving the electrophilic activation of the Si-H bond. The benchmark shows a direct dependence of the catalytic efficiency with the electronic effect of -X, which is confirmed by theoretical assessment of the intrinsic silylicities Π of hydridoiridium(III)-silylium adducts and by the theoretical evaluation of the propensity of hydridospecies to transfer the hydrido ligand to the activated substrate. The revisited analysis of the Ir-Si-H interactions shows that the most cohesive bond in hydridoiridium(III)-silylium adducts is the Ir-H one, while the Ir-Si is a weak donor-acceptor dative bond. The Si…H interaction in all the cases is noncovalent in nature and dominated by electrostatics confirming the heterolytic cleavage of the hydrosilane's Si-H bond in this key catalytically relevant species.<br /> (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Details

Language :
English
ISSN :
1521-3765
Volume :
29
Issue :
43
Database :
MEDLINE
Journal :
Chemistry (Weinheim an der Bergstrasse, Germany)
Publication Type :
Academic Journal
Accession number :
37195577
Full Text :
https://doi.org/10.1002/chem.202300811