398466-03-0Relevant articles and documents
Fluorous bulk membranes for potentiometric sensors with wide selectivity ranges: Observation of exceptionally strong ion pair formation
Boswell, Paul G.,Buehlmann, Philippe
, p. 8958 - 8959 (2005)
Potentiometric sensors based on fluorous membranes doped with a fluorophilic tetraphenylborate derivative are shown to have a remarkably wide range of selectivities that exceeds the selectivity range of conventional polymeric membranes by 8 orders of magnitude. The fluorous character of these sensing membranes explains the formation of ion pairs of unprecedented strength. Ion pair formation constants in perfluoroperhydrophenanthrene, as measured in this work, are on the order of 1020 and exceed previously reported values for ion pair formation in nonpolar solvents by 6 orders of magnitude. The low solubility of lipids in such fluorous phases makes them very promising for the reduction of biofouling. Copyright
Compensation of London Dispersion in the Gas Phase and in Aprotic Solvents
Pollice, Robert,Fleckenstein, Felix,Shenderovich, Ilya,Chen, Peter
, p. 14281 - 14288 (2019)
The importance of London dispersion for structure and stability of molecules with less than about 200 atoms has been established in recent years but the quantitative understanding is still largely based on computations because of a persistent lack of suitable experimental data. We herein report a comprehensive computational and experimental study of the compensation of London dispersion in proton-bound dimer dissociations showing that total compensation is largely invariant in both polar and nonpolar aprotic solvents spanning a wide range of bulk polarizabilities. Additionally, we find that compensation by solvent (which is about 40–80 %) largely dominates over compensation in the gas phase (which is about 0–40 %) for typical experimental temperatures.
New media for classical coordination chemistry: Phase transfer of Werner and related polycations into highly nonpolar fluorous solvents
Ghosh, Subrata K.,Ojeda, Ann Sullivan,Guerrero-Leal, Juan,Bhuvanesh, Nattamai,Gladysz, John A.
, p. 9369 - 9378 (2013/09/12)
Optimized procedures for the previously reported conversions of 1,3-diiodobenzene and perfluorohexyliodide (Rf6I; copper, DMSO, 140 C) to 1,3-C6H4(Rf6)2 (3; 86-70%) and 3 to Br(3,5-C6H3(Rf6)2 (2; NBS, H2SO4/CF3CO2H; 88-75%) are described. The latter is converted (t-BuLi, BCl3) to the fluorous BArf salt NaB(3,5-C6H 3(Rf6)2)4 (1 or NaBArf6; 77-70%), as given earlier. When orange aqueous solutions of [Co(en) 3]Cl3 (en = ethylenediamine) are treated with perfluoro(methylcyclohexane) (PFMC) solutions of 1 (1:3 mol ratio), the aqueous phase decolorizes and [Co(en)3](BArf6)3 can be isolated from the fluorous phase (96%). Similar reactions with the trans-1,2-cyclohexanediamine analogue [Co(R,R-chxn)3]Cl3 and [Ru(bipy)3]Cl2 give [Co-(R,R-chxn)3] (BArf6)3 (92%) and [Ru(bipy)3](BAr f6)2 (95%). All of these salts are isolated as hydrates and exhibit toluene/PFMC partition coefficients of ≤1:≥99, establishing that the anion BArf6- can efficiently transport polar polycations into highly nonpolar fluorous phases. When equal volumes of CH 2Cl2 and PFMC are charged with the nonfluorous BArf (B(3,5-C6H3-(CF3) 2)4) salt [Co(en)3](BArf) 3 and 3.0 equiv of the fluorous salt NaBArf6, the cobalt trication partitions predominantly into the fluorous phase (64:36). The arene 2 crystallizes in a polar space group (tetragonal, I4, Z = 8) with fluorous and nonfluorous domains and all eight bromine atoms located essentially on one face of the unit cell.
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.
Tetrakis{3,5-bis(perfluorohexyl)phenyl}borate: A highly fluorous anion
Van Den Broeke, Joep,Deelman, Berth-Jan,Van Koten, Gerard
, p. 8085 - 8087 (2007/10/03)
In search of new possibilities for rendering catalysts soluble in fluorous solvents, the preparation of a sodium derivative of tetrakis{3,5-bis(perfluorohexyl)phenyl}borate, a new and highly fluorous anion, is described. This weakly coordinating anion exhibits substantial affinity for perfluorinated solvents and is therefore expected to make a broad range of cationic transition-metal catalysts compatible with fluorous biphasic recycling techniques.
