124389-29-3Relevant academic research and scientific papers
Tetrakis{3,5-bis(perfluorohexyl)phenyl}borate: A highly fluorous anion
Van Den Broeke, Joep,Deelman, Berth-Jan,Van Koten, Gerard
, p. 8085 - 8087 (2001)
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.
Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization
Schnitte, Manuel,Scholliers, Janine S.,Riedmiller, Kai,Mecking, Stefan
, p. 3258 - 3263 (2020)
In various nickel(II) salicylaldiminato ethylene polymerization catalysts, which are a versatile mechanistic probe for substituent effects, longer perfluoroalkyl groups exert a strong effect on catalytic activities and polymer microstructures compared to the trifluoromethyl group. This effect is accounted for by a reduced electron density on the active sites, and is also supported by electrochemical studies. Thus, β-hydride elimination, the key step of chain transfer and branching pathways, is disfavored while chain-growth rates are enhanced. This enhancement occurs to an extent that enables living polymerizations in aqueous systems to afford ultra-high-molecular-weight polyethylene for various chelating salicylaldimine motifs. These findings are mechanistically instructive as well as practically useful for illustrating the potential of perfluoroalkyl groups in catalyst design.
Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds: the role of iodine Lewis basicity
Mukherjee, Tathagata,Biswas, Soumik,Ehnbom, Andreas,Ghosh, Subrata K.,El-Zoghbi, Ibrahim,Bhuvanesh, Nattamai,Bazzi, Hassan S.,Gladysz, John A.
supporting information, p. 2486 - 2501 (2017/12/06)
The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols RfnCH2OH (Rfn = CF3(CF2)n-1; n = 11, 13, 15) are converted to the triflates RfnCH2OTf (Tf2O, pyridine; 22-61%) and then to RfnCH2I (NaI, acetone; 58-69%). Subsequent reactions with NaOCl/HCl give iodine(III) dichlorides RfnCH2ICl2 (n = 11, 13; 33-81%), which slowly evolve Cl2. The ethereal fluorous alcohols CF3CF2CF2O(CF(CF3)CF2O)xCF(CF3)CH2OH (x = 2-5) are similarly converted to triflates and then to iodides, but efforts to generate the corresponding dichlorides fail. Substrates lacking a methylene group, RfnI, are also inert, but additions of TMSCl to bis(trifluoroacetates) RfnI(OCOCF3)2 appear to generate RfnICl2, which rapidly evolve Cl2. The aromatic fluorous iodides 1, 3-Rf6C6H4I, 1, 4-Rf6C6H4I, and 1, 3-Rf10C6H4I are prepared from the corresponding diiodides, copper, and RfnI (110-130 °C, 50-60%), and afford quite stable RfnC6H4ICl2 species upon reaction with NaOCl/HCl (80-89%). Iodinations of 1, 3-(Rf6)2C6H4 and 1, 3-(Rf8CH2CH2)2C6H4 (NIS or I2/H5IO6) give 1, 3, 5-(Rf6)2C6H3I and 1, 2, 4-(Rf8CH2CH2)2C6H3I (77-93%). The former, the crystal structure of which is determined, reacts with Cl2 to give a 75:25 ArICl2/ArI mixture, but partial Cl2 evolution occurs upon work-up. The latter gives the easily isolated dichloride 1, 2, 4-(Rf8CH2CH2)2C6H3ICl2 (89%). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.
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.
POLYFLUOROALKYLATION OF BROMOAROMATIC COMPOUNDS VIA PERFLUOROALKYLCOPPER INTERMEDIATES
Chen, Grace J.,Tamborski, Christ
, p. 207 - 228 (2007/10/02)
Cross coupling reactions between various perfluoroalkyl iodides, copper and mono and dibromobenzenes, as well as mono and dibromobenzenes containing functional groups e.g., OH, CO2H, CO2R, NO2, NH2, OCH3 and C(O)CH3 have produced perfluoroalkyl substituted aromatic compounds in good to excellent yields.From certain bromo arenes, by-products were obtained, indicating competing reactions.These reactions may be due to the slower rate of cross coupling between a carbon-bromine bond and the perfluoroalkylcopper intermediate as compared to the cross coupling reaction involving a carbon-iodine bond with the perfluoroalkylcopper intermediate.
