The Role of the Fluoro–Hydrido–Phosphorane Intermediate in Catalytic Hydrosilylation of Acetophenone: Computational Study

Arseni Kostenko*, Roman Dobrovetsky

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The fluorophosphonium cation [(C6F5)3PF]+ (1) is used as a catalyst in many chemical transformations including the hydrosilylation of ketones. In these reactions the fluoro–hydrido–phosphorane (C6F5)3PFH, which is formed upon a hydride abstraction by 1 from a hydrosilane, was proposed as the key intermediate. One of the most important features attributed to (C6F5)3PFH in the catalytic hydrosilylation of ketones is its ability to transfer the hydride to an electrophile. However, (C6F5)3FPH was not observed experimentally and its properties and in particular its hydride-donating ability was not studied in detail. In this work the mode of formation of (C6F5)3FPH, its properties and its interactions with substrates in the catalytic hydrosilylation of acetophenone were investigated by density functional theory (DFT), and possible routes of this catalytic reaction were studied. Calculations show that (C6F5)3PFH can act both as a fluoride and hydride donor, and that these processes can exist in thermodynamic equilibrium. However, only the donation of the hydride results in intermediates that allow the catalytic cycle to proceed.

Original languageEnglish
Pages (from-to)318-322
Number of pages5
JournalEuropean Journal of Organic Chemistry
Volume2019
Issue number2
DOIs
StatePublished - 23 Jan 2019

Funding

FundersFunder number
Tel Aviv University

    Keywords

    • Density functional calculations
    • Electrophilic phosphonium cations
    • Frustrated Lewis pairs
    • Hydrosilylation
    • Reaction mechanisms

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