New media for classical coordination chemistry: phase transfer of Werner and related polycations into highly nonpolar fluorous solvents. Academic Article uri icon


  • 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-C6H3(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](BArf6)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 CH2Cl2 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.

published proceedings

  • Inorg Chem

altmetric score

  • 0.25

author list (cited authors)

  • Ghosh, S. K., Ojeda, A. S., Guerrero-Leal, J., Bhuvanesh, N., & Gladysz, J. A.

citation count

  • 16

complete list of authors

  • Ghosh, Subrata K||Ojeda, Ann Sullivan||Guerrero-Leal, Juan||Bhuvanesh, Nattamai||Gladysz, John A

publication date

  • August 2013