Chemistry Publications
Origin of Stability and Inhibition of Cooperative Alkyne Hydrofunctionalization Catalysts
Document Type
Article
Publication Date
7-5-2021
Journal
Chemistry Europe
URL with Digital Object Identifier
10.1002/cctc.202100622
Abstract
New entries to the [Ru(Cp/Cp*)(PR2NR′2)(MeCN)]PF6 catalyst family were synthesized, including a Cp complex (R = Cy; R′ = Ph) and two Cp* complexes (R = Cy, Ph; R′ = Ph). These and other derivatives were used for the intramolecular hydroamination of 2-ethynylaniline to elucidate trends in catalytic lifetime and rate. The readily accessible [Ru(Cp)(PCy2NPh2)(MeCN)]PF6 derivative showed comparable lifetime to [Ru(Cp)(Pt−Bu2NPh2)(MeCN)]PF6, the previous optimal catalyst. Donor-free ‘active’ catalysts, [Ru(Cp/Cp*)(PCy2NPh2)]PF6, were prepared and their thermal stability was assessed. The relatively high stability of the Cp derivative was explained by the capacity of the PCy2NPh2 ligand to coordinate in a κ3-(P,P,Ar) mode, which protects the low-coordinate species. This coordination mode is inaccessible with the Cp* derivative. Additionally, [Ru(Cp*)(PCy2NPh2)]PF6 readily activated the C−Cl bond of the solvent dichloromethane. Variable time normalization analysis (VTNA) revealed that the indole product inhibited the catalyst [Ru(Cp)(PCy2NPh2)(MeCN)]PF6, which slowed catalytic rates.
Citation of this paper:
Chapple, D.E., Boyle, P.D. and Blacquiere, J.M. (2021), Origin of Stability and Inhibition of Cooperative Alkyne Hydrofunctionalization Catalysts. ChemCatChem. https://doi.org/10.1002/cctc.202100622