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1 This journal is The Royal Society of Chemistry 212 Supplementary Information for: Ruthenium nanoparticle catalysts stabilized in phosphonium and imidazolium ionic liquids: Dependence of catalyst stability and activity on the ionicity of the ionic liquid Kylie L. Luska a and Audrey Moores* a a Centre for Catalysis and Green Chemistry, Department of Chemistry, McGill University, Otto Maass Chemistry Building, 81 Sherbrooke Street West, Montreal, Quebec, Canada, H3A B8.
2 This journal is The Royal Society of Chemistry 212 Transmission Electron Microscopic Data Fig. S1 TEM images for Ru NPs before catalysis prepared in (A) [P 4,4,4,1 ]NTf 2, (B) [P 4,4,4,8 ]NTf 2, (C) [P 4,4,4,14 ]NTf 2, (D) [P 4,4,4,1 ]OTf, (E) [P 4,4,4,1 ]PF 6, (F) [P 4,4,4,1 ]Cl, (G) [BMI]NTf 2 and (H) [BDMI]NTf 2.
3 This journal is The Royal Society of Chemistry A B C 5 4 D E 4 35 F G H Fig. S2 TEM histograms for Ru NPs before catalysis prepared in (A) [P 4,4,4,1 ]NTf 2, (B) [P 4,4,4,8 ]NTf 2, (C) [P 4,4,4,14 ]NTf 2, (D) [P 4,4,4,1 ]OTf, (E) [P 4,4,4,1 ]PF 6, (F) [P 4,4,4,1 ]Cl, (G) [BMI]NTf 2 and (H) [BDMI]NTf 2.
4 This journal is The Royal Society of Chemistry 212 Fig. S3 TEM images for Ru NPs after catalysis prepared in (A) [P 4,4,4,1 ]NTf 2, (B) [P 4,4,4,8 ]NTf 2, (C) [P 4,4,4,14 ]NTf 2, (D) [P 4,4,4,1 ]OTf, (E) [P 4,4,4,1 ]PF 6, (F) [P 4,4,4,1 ]Cl, (G) [BMI]NTf 2 and (H) [BDMI]NTf 2.
5 This journal is The Royal Society of Chemistry A 5 4 B C 6 5 D E 6 5 F N/A More G H Fig. S4 TEM histograms for Ru NPs after catalysis prepared in (A) [P 4,4,4,1 ]NTf 2, (B) [P 4,4,4,8 ]NTf 2, (C) [P 4,4,4,14 ]NTf 2, (D) [P 4,4,4,1 ]OTf, (E) [P 4,4,4,1 ]PF 6, (F) [P 4,4,4,1 ]Cl, (G) [BMI]NTf 2 and (H) [BDMI]NTf 2.
6 This journal is The Royal Society of Chemistry 212 Walden Plot Data Table S1. Experimental Density ( exp ) for Phosphonium and Imidazolium Ionic Liquids as a Function of Temperature (T) Ionic Liquid exp (g cm -3 ) at T (K) [P 4,4,4,1 ]NTf [P 4,4,4,8 ]NTf [P 4,4,4,14 ]NTf [BMI]NTf [BDMI]NTf Table S2. Calculated Density ( calc ) for Phosphonium and Imidazolium Ionic Liquids as a Function of Temperature (T) Employing the Parameters of the Linear Fit ( exp = at - b) Ionic Liquid Parameters calc (g cm -3 ) at T (K) a b [P 4,4,4,1 ]NTf [P 4,4,4,8 ]NTf [P 4,4,4,14 ]NTf [BMI]NTf [BDMI]NTf Table S3. Experimental Viscosity ( ) for Phosphonium and Imidazolium Ionic Liquids as a Function of Temperature (T) Ionic Liquid (mpa s) at T (K) [P 4,4,4,1 ]NTf [P 4,4,4,8 ]NTf [P 4,4,4,14 ]NTf [BMI]NTf [BDMI]NTf
7 This journal is The Royal Society of Chemistry 212 Table S4. Specific Conductivity ( ) for Phosphonium and Imidazolium Ionic Liquids as a Function of Temperature (T) Ionic Liquid (ms cm -1 ) at T (K) [P 4,4,4,1 ]NTf [P 4,4,4,8 ]NTf [P 4,4,4,14 ]NTf [BMI]NTf [BDMI]NTf Table S5. Calculated Molar Conductivity ( m ) for Phosphonium and Imidazolium Ionic Liquids as a Function of Temperature (T) Ionic Liquid m (S cm 2 mol -1 ) at T (K) [P 4,4,4,1 ]NTf [P 4,4,4,8 ]NTf [P 4,4,4,14 ]NTf [BMI]NTf [BDMI]NTf The molar conductivity was calculated according to: m M where is the specific conductivity, M is the molar mass and is the density. Table S6. Deviation from the Ideal Line ( W) as a Function of Temperature (T) and the Fitting Parameters for the Fractional Walden Plot (log m = log C + log -1 ) for Phosphonium and Imidazolium Ionic Liquids Ionic Liquid Parameters W at T (K) log C [P 4,4,4,1 ]NTf [P 4,4,4,8 ]NTf [P 4,4,4,14 ]NTf [BMI]NTf [BDMI]NTf
8 This journal is The Royal Society of Chemistry 212 Nuclear Magnetic Resonance Data Fig. S5 1 H NMR spectrum of tetradecyl(tributyl)phosphonium methanesulfonate, [P 4,4,4,14 ]O 3 SMe, in CDCl 3 obtained using a 3 MHz spectrometer. Fig. S6 13 C NMR spectrum of tetradecyl(tributyl)phosphonium methanesulfonate, [P 4,4,4,14 ]O 3 SMe, in CDCl 3 obtained using a 75.5 MHz spectrometer.
9 This journal is The Royal Society of Chemistry 212 Fig. S7 31 P NMR spectrum of tetradecyl(tributyl)phosphonium methanesulfonate, [P 4,4,4,14 ]O 3 SMe, in CDCl 3 obtained using a 81. MHz spectrometer. Fig. S8 1 H NMR spectrum of tetradecyl(tributyl)phosphonium bis(trifluoromethylsulfonyl)amide, [P 4,4,4,14 ]NTf 2, in CDCl 3 obtained using a 3 MHz spectrometer.
10 This journal is The Royal Society of Chemistry 212 Fig. S9 13 C NMR spectrum of tetradecyl(tributyl)phosphonium bis(trifluoromethylsulfonyl)amide, [P 4,4,4,14 ]NTf 2, in CDCl 3 obtained using a 75.5 MHz spectrometer. Fig. S1 31 P NMR spectrum of tetradecyl(tributyl)phosphonium bis(trifluoromethylsulfonyl)amide, [P 4,4,4,14 ]NTf 2, in CDCl 3 obtained using a 81. MHz spectrometer.
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