874161-81-6Relevant articles and documents
Systematic Study of the Stereoelectronic Properties of Trifluoromethylated Triarylphosphines and the Correlation of their Behaviour as Ligands in the Rh-Catalysed Hydroformylation
Herrera, Daniel,Peral, Daniel,Cordón, Mercedes,Bayón, J. Carles
, p. 354 - 363 (2021)
The stereoelectronic properties of a series of trifluoromethylated aromatic phosphines have been studied using different approaches. The σ-donating capability has been evaluated by nuclear magnetic resonance (NMR) spectroscopy of the selenide derivatives and the protonated form of the different trifluoromethylated phosphines. The coupling constants between phosphorous and selenium (1JSeP) and phosphorous and hydrogen (1JHP) can be predicted by empirical equations and correlate the basicity of the phosphines with the number and relative position of trifluoromethyl groups. In contrast, the π-acceptor character of the ligands has been evaluated by measuring the frequency of the CO vibration in the infrared (IR) spectra of the corresponding Vaska type iridium complexes ([IrCl(CO)(PAr3)2], PAr3=triarylphosphine). Moreover, the correlation between the electronic properties and the performance of these phosphines as ligands in the rhodium-catalysed hydroformylation of 1-octene has been established. Phosphines with the lowest basicity, that are those with the highest number of trifluoromethyl groups, gave rise to more active catalytic systems.
Anionic Palladium(0) and Palladium(II) Ate Complexes
Kolter, Marlene,B?ck, Katharina,Karaghiosoff, Konstantin,Koszinowski, Konrad
supporting information, p. 13244 - 13248 (2017/10/17)
Palladium ate complexes are frequently invoked as important intermediates in Heck and cross-coupling reactions, but so far have largely eluded characterization at the molecular level. Here, we use electrospray-ionization mass spectrometry, electrical cond
Rhodium catalysed hydroformylation of alkenes using highly fluorophilic phosphines
Adams, Dave J.,Bennett, James A.,Cole-Hamilton, David J.,Hope, Eric G.,Hopewell, Jonathan,Kight, Jo,Pogorzelec, Peter,Stuart, Alison M.
, p. 3862 - 3867 (2007/10/03)
Highly fluorophilic phosphines incorporating at least one aromatic ring containing two directly attached perfluoroalkyl groups have been synthesised, their partition coefficients (organic phase : fluorous phase) measured and their electronic properties probed using 1JPtP data for their trans-[PtCl2L2] complexes. These phosphines have been used as modifying ligands for the rhodium catalysed hydroformylation of 1-octene in perfluorocarbon solvents. Catalyst activity, regioselectivity and the levels of rhodium leaching to the product phase vary with the substitution patterns of the modifying ligands that do not correlate with the electronic properties or partition coefficients of these ligands, but can be interpreted in terms of differences in the resting states of the catalysts. The Royal Society of Chemistry 2005.
