1. Reactivity of Tantalum/Iridium and Hafnium/Iridium Alkyl Hydrides with Alkyl Lithium Reagents: Nucleophilic Addition, Alpha-H Abstraction, or Hydride Deprotonation?
- Author
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Sébastien Lassalle, Julien Petit, Rosalyn L. Falconer, Valentin Hérault, Erwann Jeanneau, Chloé Thieuleux, Clément Camp, Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de diffractométrie Henri Longchambon, Institut de Chimie de Lyon, École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, and ANR-21-CE07-0009,SHICC,Sites Hétérobimétalliques Isolés pour une Catalyse Coopérative(2021)
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Inorganic Chemistry ,Organic Chemistry ,[CHIM]Chemical Sciences ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,Physical and Theoretical Chemistry - Abstract
International audience; Cp*IrH 4 reacts with Hf(Np) 4 (Np = CH 2 C(CH 3) 3) to yield the heterobimetallic complex [Hf(Np) 3 (μ-H) 3 IrCp*], 2. Treatment of 2 with neopentyl lithium (NpLi) results in the nucleophilic addition of a neopentyl moiety onto the Hf center, restoring Hf(Np) 4 and displacing the Cp*IrH 3 iridate fragment. By contrast, treatment of the tantalum/iridium analogue, [Ta(Np) 3 IrH 2 (Cp*)], 1, with NpLi triggers the α-hydrogen abstraction at a Ta-neopentyl moiety and leads to the formation of the alkylidene-ate complex [Li][{Ta(CH t Bu)(Np) 2 }{IrH 2 Cp*}], 4. The benzylidene analogue, [K][{Ta(CHPh)(Np) 2 }{IrH 2 Cp*}], 5, is obtained upon reacting 1 with benzyl potassium. An unusual vinyl oxo species, [{Li(THF) 3 }Ta(O)(Np) 2 {μ-C 2 H 3 }IrH(Cp*)], 6, is formed when the reaction of 1 with NpLi is carried out in THF, due to THF fragmentation.
- Published
- 2022
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