Ruthenium-Based Metathesis Catalysts
recorded with a recycle time of 5 s. A 4 µs pulse was used.
The RF field was 63 kHz. Chemical shifts for phosphorus are
reported relative to (NH4)H2PO4 at 1.11 ppm.
CHOAr, J ) 6.0), 3.98 (s, 4 H, N(CH2)2N), 2.36 (s, 6 H, mesityl
p-CH3), 2.03 (s, 12 H, mesityl o-CH3), 0.98 (d, 6 H, (CH3)2-
CHOAr, J ) 6.0). 13C{1H}-NMR (CDCl3): δ 313.5, 211.6, 160.7,
153.7, 144.8, 143.8, 139.2, 134.8, 129.6, 129.5, 128.6, 126.5,
123.5, 122.6, 111.0, 74.4, 51.3, 21.1, 20.0, 17.9. ESI-MS
(acetonitrile/water) calcd for C45H38N2F10O5Ru: 978.17, found
782.9 (M+• + H+ - C6F5CO, 33), 307.4 (IMesH2 + H+, 29). Anal.
Calcd for C45H38N2F10O5Ru: C, 55.21; H, 3.92; N, 2.86.
Found: C, 54.93; H, 4.30; N, 2.53.
RCM Experiments. Reactions were run for 18 h in order
to achieve complete conversion. For the homogeneous catalysts,
a carousel working station under N2 was used. The reaction
volume was 1-4 mL. Heterogeneous catalysts were run in a
N2-mediated drybox using microreactors in a thermo shaker.
Analyses were done by NMR after filtration for catalysts 2, 4,
and 6 and by HPLC for catalysts 8 and 10. No other products
were found.
Ru(C6F5O)2(IMesH2)(dCH-2-(2-PrO)C6H4) (7). RuCl2-
(IMesH2)(dCH-2-(2-PrO)C6H4) (200 mg, 0.32 mmol) was dis-
solved in 10 mL of THF, and a solution of TlOC6F5 (2 equiv,
260 mg, 0.64 mol), generated in situ from TlOC2H5 and C6F5-
OH in a mixture of 1 mL of THF, 1 mL of methanol, and 1 mL
of toluene, was slowly added. Stirring was continued for 3 h.
A color change from red to brown and the formation of a
precipitate was observed. The precipitate was filtered off and
the solution evaporated to dryness. The solid was redissolved
in CH2Cl2, centrifuged, and filtered through Celite. Drying in
vacuo provided a brown powder (249 mg, 0.27 mmol, 85%).
IR-ATR (cm-1): 2966 (br, s), 2921 (br, s), 1644 (w), 1617 (w),
1591 (w), 1575 (w), 1495 (vs), 1455 (vs), 1379 (w), 1294 (w),
1260 (vs), 1203 (w), 1158 (s), 1112 (s), 1106 (vs), 980 (vs), 851
(s), 794 (vs), 741 (vs), 629 (w). 1H NMR (CDCl3): δ 17.10 (s, 1
H, RudCHAr), 7.44 (dd, 1 H, aromatic CH, J1 ) 1.5, J2 ) 2.0),
7.11 (s, 4 H, mesityl CH), 7.26 (dd, 1 H, aromatic CH, J1 )
7.3, J2 ) 7.8), 6.97 (dd, 1 H, aromatic CH, J1 ) 1.5, J2 ) 1.5),
6.80 (d, 1 H, aromatic CH, J ) 8.3), 3.82 (sep, 1 H, (CH3)2-
CHOAr, J ) 6.0), 4.10 (s, 4 H, N(CH2)2N), 2.41 (s, 6 H, mesityl
p-CH3), 2.28 (s, 12 H, mesityl o-CH3), 0.67 (d, 6 H, (CH3)2-
CHOAr, J ) 6.0). 13C{1H}-NMR (CDCl3): δ 296.3, 210.4, 150.2,
143.3, 142.3, 139.3, 136.1, 129.5, 128.7, 127.8, 126.5, 123.3,
122.0, 111.4, 74.7, 51.2, 21.2, 19.3, 18.1. HRMS calcd for
C43H38N2F10O3Ru: 922.18, found 922.30.
Ru(CF3COO)2(PCy3)(dCH-2-(2-PrO)C6H4) (1). Silver tri-
fluroacetate (23.2 mg, 0.105 mmol) was suspended in 10 mL
of CH2Cl2. RuCl2(PCy3)(dCH-2-(2-PrO)C6H4) (30 mg, 0.05
mmol), dissolved in 0.5 mL of CH2Cl2, was added, and the
solution was stirred for 30 min in the absence of light. The
mixture was filtered through Celite/cellulose, and the solvent
was reduced in vacuo. The product (37 mg, 0.049 mmol, 98%)
was obtained as a red, foamy solid. Recrystallization from
hexane/CH2Cl2 yielded red needles. IR (cm-1): 724 (m), 735
(m), 863 (m), 929 (w), 1144 (s), 1190 (ss), 1391 (w), 1453 (m),
1642 (m), 1712 (s), 2854 (m), 2931 (s). 1H NMR (500 MHz;
CDCl3): δ 1.22-1.33 (m, 9H), 1.45 (d, J ) 6.7, 6H), 1.48-1.58
(m, 6H), 1.67-1.76 (m, 3H), 1.78-1.95 (m, 12H), 2.02-2.12
(m, 3H), 4.96-5.05 (m, 1H), 7.03 (d, J ) 8, 1H), 7.19 (dd, J1 )
J2 ) 7.5, 1H), 7.62 (dd, J1 ) J2 ) 8, 1H), 7.80 (d, J ) 7.5, 1H),
18.39 (d, J ) 6, 1H). 13C NMR (125.8 MHz; CDCl3): δ 21.1,
26.3, 27.7, 29.0, 34.2, 34.4, 76.7, 112.7, 113.8 (q, J ) 288.5),
123.4, 124.4, 131.2, 144.2 (q), 155.22 (q), 163.48 (q, J ) 33.7),
308.5 (d, J ) 15.1). 31P NMR (202.5 MHz; CDCl3): δ 56.6. 19
F
NMR (470.6 MHz; CDCl3): δ -74.6. EI-MS (200 °C): m/z )
756 (M+), 642 (46), 600 (6), 404 (10), 375 (10), 281 (24), 243
(100%), 198 (54), 120 (62), 91 (36), 83 (54), 78 (60), 55 (75).
HR-MS calcd for C32H45F6O5PRu): 756.1946, found 756.1933.
Ru(PS-DVB-CH2OCOCF2CF2CF2COO)(CF3CO2)-
(dCHC6H5)(IMesH2)(PCy3) (8). PS-DVB-CH2OCOCF2CF2-
CF2COOAg was prepared according to the literature.31 PS-
DVB-CH2OCOCF2CF2CF2COOAg (500 mg) was suspended in
CH2Cl2 (15 mL), and RuCl2(dCHC6H5)(IMesH2)(PCy3) (80 mg,
0.094 mmol), dissolved in CH2Cl2 (2 mL), was added slowly.
The mixture was stirred for 90 min in the absence of light,
and CF3COOAg (21 mg, 0.094 mmol), dissolved in 2 mL of
THF, was added. The reaction mixture was stirred for a
further 90 min. The product was filtered and washed three
times with THF (10 mL) until the filtrate was colorless. Drying
in vacuo provided a red-lilac powder (450 mg). IR-ATR (cm-1):
3082 (w), 3058 (w), 3024 (s), 2918 (br), 2849 (w), 1869 (w),
1773 (br), 1660 (br), 1601 (s), 1510 (s), 1492 (s), 1308 (w), 1265
Ru(CF3COO)2(dCHC6H5)(IMesH2)(PCy3) (3). CF3COOAg
(10 mg, 0,043 mmol) was suspended in 10 mL of CH2Cl2 and
stirred for 5 min. A solution of RuCl2(dCH-C6H5)(IMesH2)-
(PCy3) (17.8 mg, 0.021 mmol) in 2 mL of CH2Cl2 was added.
Stirring was continued for 5 min. A color change from red to
green-brown and the formation of a precipitate was observed.
The precipitate was filtered off, and the solution was filtered
through Celite. Drying in vacuo provided a red powder. No
satisfying elemental analysis was obtained due to coprecipi-
tation of AgCl‚PCy3. Yield: 18.5 mg (0.018 mmol, 85%). IR-
ATR (cm-1): 2925 (s), 2851 (s), 1686 (s), 1631 (s), 1482 (s),
1448 (s), 1265 (s), 1192 (vs), 1136 (vs), 1030 (w), 1003 (w), 962
(vw), 851 (s), 785 (w), 737 (vs), 695 (s), 618 (vw). 1H NMR
(CDCl3): δ 18.34 (s, 1 H, RudCH), 7.45 (d, 1 H, J ) 5.5), 7.27
(m, 4 H), 6.93 (d, 1H, J ) 6.3), 6.77 (m, 2 H), 4.09 (s, 4 H),
2.17 (m, 17 H), 1.80 (s, 20 H), 1.19 (m, 20 H). 13C NMR
(CDCl3): δ 289.2, 184.4, 159.6, 140.7, 137.3, 135.4, 134.7, 129.7,
128.7, 127.8, 52.0, 31.9, 29.0, 27.8, 26.2, 20.8, 17.7, 14.1.
Additional signals for AgCl‚PCy3: 31.2, 27.1, 25.8. 31P{1H}-
NMR (CDCl3): δ ) 41.2, 45.1 (AgCl‚PCy3).
1
(s), 1154 (br), 1029 (br), 908 (w), 819 (w), 751 (s), 697 (s). H-
MAS NMR: δ 6.99 (br), 3.79 (sh), 1.95 (sh). 13C-CP-MAS
NMR: δ 18.5, 21.3 (sh), 26.0, 40.6, 45.7 (sh), 65.1, 68.1, 128.1,
139.4, 145.6. 31P-MAS NMR: δ 41.1. ICP-OES: 0.22 mg Ru/
g. Anal. Found: C, 75.24; H, 6.45; N, 0.47.
Ru(PS-DVB-CH2OCOCF2CF2CF2COO)(CF3CO2)(dCH-
2-(2-PrO)C6H4)(PCy3) (9). PS-DVB-CH2OCOCF2CF2CF2-
COOAg (850 mg) was suspended in CH2Cl2 (25 mL), and
RuCl2(dCH-2-(2-PrO)C6H4)(PCy3) (95.5 mg, 0.152 mmol) in
CH2Cl2 (2 mL) was added. The mixture was stirred for 90 min
in the absence of light. CF3COOAg (35.2 mg, 0.152 mmol) was
dissolved in THF (2 mL) and added to the catalyst. Stirring
was continued for another 90 min. The product was filtered
and washed three times with THF (10 mL) until the filtrate
was colorless. Drying in vacuo provided a red-lilac powder (650
mg). IR (cm-1): 3082 (w), 3058 (w), 3024 (s), 2919 (br), 2849
(w), 1939 (w), 1773 (br), 1656 (br), 1510 (s), 1451 (s), 1308 (w),
1154 (br), 1029 (br), 907 (w), 819 (w), 749 (s), 697 (s). 1H-MAS
NMR δ 7.34 (br), 4.05 (sh), 2.00 (sh). 13C-CP-MAS NMR δ 40.7,
45.2 (sh), 65.1, 68.1, 128.0, 146.0. 31P-MAS NMR δ 56.81 (d).
ICP-OES: 2.62 mg Ru/g. Anal. Found: C, 73.55; H, 6.36.
Ru(C6F5CO2)2(IMesH2)(dCH-2-(2-PrO)C6H4) (6). RuCl2-
(IMesH2)(dCH-2-(2-PrO)C6H4) (200 mg, 0.32 mmol) was dis-
solved in 10 mL of THF, and a solution of TlCO2C6F5 (2 equiv,
266 mg, 0.64 mmol), generated in situ from TlOC2H5 and C6F5-
CO2H in a mixture of 1 mL of THF, 1 mL of methanol, and 1
mL of toluene, was slowly added. Stirring was continued for 3
h. A color change from red to brown and the formation of a
precipitate was observed. The precipitate was filtered off and
the solution evaporated to dryness. The solid was redissolved
in CH2Cl2, centrifuged, and flashed over Celite. Drying in
vacuo provided a lilac powder (272 mg, 0.28 mmol, 87%). IR
(cm-1): 2924 (br), 1663 (vs), 1594 (w), 1517 (s), 1479 (vs), 1333
(vs), 1267 (vs), 1210 (w), 1098 (s), 1034 (w), 987 (vs), 920 (s),
1
878 (w), 842 (w), 745 (vs), 699 (s), 574 (s). H NMR (CDCl3):
δ 17.33 (s, 1 H, RudCHAr), 7.43 (d, 1 H, aromatic CH, J )
9.0), 7.01 (s, 4 H, mesityl CH), 7.23 (dd, 1 H, aromatic CH, J1
) 7.5, J2 ) 9.0), 6.83 (dd, 1 H, aromatic CH, J1 ) 7.5, J2 7.3),
6.59 (d, 1 H, aromatic CH, J ) 8.3), 4.57 (sep, 1 H, (CH3)2-
(31) Yang, L.; Mayr, M.; Wurst, K.; Buchmeiser, M. R. Chem. Eur.
J. 2004, 10, 5761-5770.
J. Org. Chem, Vol. 70, No. 12, 2005 4693