250
N. Marozsán et al. / Molecular Catalysis 445 (2018) 248–256
2.5. Synthesis of [RuCl(emim)(ꢀ6-p-cymene)(PPh3)]Cl (7)
(Procedure S1.4)
triturated several times with small portions of cold diethyl ether
until it solidified giving 4 as orange yellow powder. Dried under
argon. Yield: 470 mg (66%). The product can be recrystallized from
CH2Cl2 by layering hexane on top of the solution; crystals for single
crystal X-ray diffraction measurements were also obtained using
this procedure.
Under argon, 30 mg (7.20 × 10−2 mmol) [RuCl2(emim)(6-p-
cymene)] (4) was dissolved in 5 mL dry methanol. To the resulting
orange yellow solution 18.9 mg (7.20 × 10−2 mmol) powdered PPh3
was added in one portion. The solution was stirred for 2 h at room
temperature followed by filtering it through Hyflo® Super-Cel® fil-
ter aid. The solvent was removed by evaporation under vacuum
yielding a sticky residue which was kept overnight in the freezer
compartment of a refrigerator. Next day the solid was washed with
diethyl ether (3 × 5 mL) and triturated with small portions of cold
diethyl ether until it solidified giving 7 as orange yellow powder.
Dried under argon. Yield 37.5 mg (77%). The product can be recrys-
tallized from CH2Cl2 by layering hexane on top of the solution.
Elemental analysis (as PF6 salt, 7·PF6; %). Found: C, 51.93; H, 4.86; N,
3.35; Calculated for C34H39N2P2ClF6Ru: C, 51.81; H, 4.99; N, 3.55%.
ESI-MS (CH3OH): m/z 643.160 ([M]+, calc. 643.158); correct iso-
tope distribution pattern (Fig. S21).
Elemental analysis (%). Found: C, 45.98; H, 5.67; N, 6.69%; Cal-
culated for C16H24N2Cl2Ru: C, 46.15; H, 5.81; N, 6.72%.
ESI-MS (CH3OH): m/z 381.065 ([M-Cl]+, calc. 381.067); correct
isotope distribution pattern (Fig. S5).
1H NMR (360 MHz, 298 K, CD2Cl2) ␦/ppm 1.16 (d, 6H,
CH3 CH CH3), 1.33 (t, 3H, N CH2CH3), 1.89 (s, 3H, C CH3), 2.84
(heptet, 1H, CH3 CH-CH3), 3.87 (s, 3H, N CH3), 4.17 (quartet, 2H,
N
N
CH2CH3), 4.96 (d, 2H, −CH-), 5.30 (d, 2H, −CH-), 7.00 (d, 1H,
CH CH N), 7.07 (d, 1H, N CH CH-N) (Fig. S3).
13C NMR (90 MHz, 298 K, CD2Cl2) ␦/ppm 16.69 (C-CH3),
18.36 (N CH2CH3), 22.11 (CH-CH3), 30.74 (CH CH3), 39.31 (N-
CH3), 46.23(N-CH2), 81.79, 85.80 (CH-CH), 98.85 (C-CH3), 109.19
(CH CH(CH3)2), 121.18, 124.20 (N-CH CH N), 173.80 (NCN) (Fig.
S4).
1H NMR (400 MHz, 298 K, CD2Cl2) ␦/ppm 1.00 (d, 6H,
CH3 CH CH3), 1.31 (t, 3H, N CH2CH3), 1.75 (s, 3H, C CH3), 2.36
(heptet, 1H, CH3 CH-CH3), 3.06 (s, 3H, N CH3), 4.06 (quartet, 2H,
2.3. Synthesis of [RuCl2(bmim)(ꢀ6-C6H6)] (5) (Procedure S1.2)
N
CH2CH3), 5.65-5.90 (m, 4H, −CH-), 6.93 (d, 1H, N CH CH N),
7.20 (d, 1H, N CH CH N), 7.20-7.72 (m, 15H, PPh3) (Fig. S18).
13C NMR (100 MHz, 298 K, toluene-d8 (4):MeOD (1)) ␦/ppm
12.22 (C-CH3), 15.67 (N CH2CH3), 20.57 (CH-CH3), 28.62
(CH CH3), 37.73 (N-CH3), 45.34 (N-CH2), 86.17, 87.97, 88.17,
90.94 (CH-CH), 105.34 (C-CH3), 113.44 (CH CH(CH3)2), 122.76,
Complex 5 was prepared according to the procedure given
above for 4 with the following amounts of reagents: 300 mg
(1.72 mmol) bmim.HCl, 240 mg (1.03 mmol) Ag2O, 430 mg
(0.86 mmol) [{RuCl2(6-C6H6)}2]. Orange yellow powder. Yield
400 mg (60%). The product can be recrystallized from CH2Cl2 by
layering hexane on top of the solution; crystals for single crystal
X-ray diffraction measurements were also obtained using this
procedure.
3
123.08 (N-CH CH N), 128.88 (d, JP-C = 9.7 Hz, Ph, meta), 130.66
2
(d, JP-C = 9.7 Hz, Ph, ortho), 130.95 (s, Ph, para), 132.46 (d,
1JP-C = 19.4 Hz, Ph, ipso), 165.43 (d, JP-C = 19.7 Hz NCN), 165.63(d,
2
2JP-C = 19.7 Hz NCN) (Fig. S19).
Elemental analysis (%): Found: C, 43.19; H, 5.27; N, 7.06; Calcu-
lated for C14H20N2Cl2Ru: C, 43.30; H, 5.19; N, 7.21.
31P{ H} NMR (145 MHz, 298 K, CD2Cl2) ␦/ppm 24.57 (s), 31.94
1
(s), 32.94 (s) (Fig. S20).
ESI-MS (CH3OH): m/z 353.036 ([M-Cl]+, calc. 353.035); 317.056
([M-2Cl-H]+, calc. 317.059); 335.068 ([M-2Cl + OH]+, calc. 335.070);
correct isotope distribution patterns (Fig. S10).
1H NMR (400 MHz, 298 K, CD2Cl2) ␦/ppm 0.90 (t, 3H,
CH2 CH2 CH2 CH3), 1.34 (sextet, 2H,CH2 CH2 CH2 CH3), 1.70
(quintet, 2H, CH2 CH2 CH2 CH3), 3.86 (s, 3H, N CH3), 4.21 (t, 2H,
CH2 CH2 CH2 CH3), 5.44 (s, 6H, C6H6) 6.98 (d, 1H, N CH CH-N)
7.02 (d, 1H, N CH CH N) (Fig. S8).
2.6. Synthesis of [RuCl(emim)(ꢀ6-p-cymene)(pta]Cl (8)
(Procedure S1.5)
Complex
given above for
8
was prepared according to the procedure
in reaction of 90 mg (0.216 mmol)
7
13C NMR (100 MHz, 298 K, CD2Cl2) ␦/ppm 13.71
(CH2 CH2 CH2-CH3), 20.10 (CH2 CH2-CH2 CH3), 33.80 (CH2-
CH2 CH2 CH3), 39.28 (N-CH3), 51.15 (N-CH2), 86.17 (CH-CH),
121.57, 124.14 (N-CH CH N), 171.21 (NCN) (Fig. S9).
[RuCl2(emim)(6-p-cymene)] (4) and 34.1 mg (0.216 mmol)
1,3,5-triaza-7-phosphaadamantane (pta). Orange yellow powder.
Yield 95 mg (77%). The product can be purified by recrystallization
from 0.1 M HCl by layering ethanol on top of the aqueous phase.
Elemental analysis (%): Found: C, 44.13; H, 6.52; N, 10.83; Cal-
culated for C22H36PN5Cl2Ru:
2.4. Synthesis of [RuCl2(emim)(ꢀ6-C6H6)] (6) (Procedure S1.3)
C, 46.07; H, 6.33; N, 12.21. Despite our efforts we were unable
to obtain samples with more correct elemental analysis data and
the composition of the product was established on basis of NMR,
MS and X-ray diffraction analyses.
Complex 6 was prepared according to the procedure given
above for 4 with the following amounts of reagents: 252 mg
(1.72 mmol) emim.HCl, 240 mg (1.03 mmol) Ag2O, 430 mg
(0.86 mmol) [{RuCl2(6-C6H6)}2]. Orange yellow powder. Yield
280 mg (45%).
ESI-MS (CH3OH): m/z 538.143 ([M]+, calc. 538.144); correct iso-
tope distribution pattern (Fig. S27).
1H NMR (400 MHz, 298 K, CD2Cl2) ␦/ppm 1.12 (d, 6H,
CH3 CH CH3), 1.36 (t, 3H, N CH2CH3), 1.93 (s, 3H, C CH3), 2.51
(heptet, 1H, CH3 CH-CH3), 3.30 (s, 3H, N CH3), 4.12 (quartet, 2H,
Elemental analysis (%): Found: C, 40.47; H, 4.59; N, 7.30; Calcu-
lated for C12H16N2Cl2Ru: C, 40.00; H, 4.48; N, 7.78.
ESI-MS (CH3OH): m/z 325.005 ([M-Cl]+, calc. 325.004); 289.024
([M-2Cl-H]+, calc. 289.028); 307.037 ([M-2Cl + OH]+, calc. 307.038);
correct isotope distribution patterns (Fig. S15).
N
CH2CH3), 4.32 (m, 6H, PCH2N), 4.36 (m, 6H, NCH2N), 5.70 (d, 1H,
−CH-), 5.85 (d, 1H, −CH-), 6.17 (d, 1H, −CH-), 6.27 (d, 1H, −CH-),
1H NMR (500 MHz, 298 K, CD2Cl2) ␦/ppm 1.33 (t, 3H,
7.17-7.35 (m, 2H, N CH CH-N) (Fig. S24).
13C NMR (100 MHz, 298 K, CD2Cl2) ␦/ppm 16.91 (C-CH3), 18.32
(N CH2CH3), 23.44 (CH-CH3), 31.21 (CH CH3), 40.33 (N-CH3),
46.79 (N-CH2), 52.32 (d, 1JP-C = 17 Hz, PCH2N), 72.93 (d, 3JP-C = 6 Hz,
NCH2N), 87.21, 87.77, 90.67, 91.80 (CH-CH), 102.69 (C-CH3), 114.30
(CH CH(CH3)2), 123.40, 123.98 (N-CH CH N), 168.91, 169.12,
169.39 (NCN) (Fig. S25).
N
CH2CH3), 3.88 (s, 3H, N CH3), 4.17 (quartet, 2H, N CH2CH3),
5.44 (s, 6H, C6H6), 6.98 (d, 1H, N CH CH N), 7.02 (d, 1H,
N
CH CH-N) (Fig. S13).
13C NMR (125 MHz, 298 K, CD2Cl2) ␦/ppm 16.75 (N CH2CH3),
39.26 (N-CH2CH3), 46.19 (N-CH3), 86.16 (CH-CH), 121.22, 124.22
(N-CH CH N), 171.35 (NCN) (Fig. S14).