IPr* vs IPr in ruthenium olefin metathesis
Simone Manzini, César A. Urbina Blanco and Steven P. Nolan*
Supporting Information
General informations: .......................................................................................................................... 2 Synthesis of [RuCl2(IPr*)(PPh3)(3-phenylindenylidene)](1): ............................................................. 2 Synthesis of [RuCl2(IPr*)(Py)(3-phenylindenylidene)](2): ............................................................... 23 Synthesis of [RuCl2(IPr)(PPh3)(3-phenylindenylidene)](3): ............................................................... 3 Synthesis of [RuCl2(IPr)(Py)(3-phenylindenylidene)](4): ................................................................. 34 General procedure for RCM and Enyne reactions: .............................................................................. 4 General procedure for CM reactions:................................................................................................. 45 NMR data of [RuCl2(IPr*)(PPh3)(3-phenylindenylidene)] (1): ........................................................... 5 NMR data of [RuCl2(IPr*)(Py)(3-phenylindenylidene)] (2): .............................................................. 6 NMR data of [RuCl2(IPr)(PPh3)(3-phenylindenylidene)] (3): ............................................................. 7 NMR data of [RuCl2(IPr)(Py)(3-phenylindenylidene)] (4): ................................................................ 8 REFERENCES................................................................................................................................... 10
General informations: All reagents were used as received. Dichloromethane and toluene were dispensed from a solvent purification system from Innovative Technology. Catalyst syntheses were performed in a MBraun glovebox containing dry Ar and less than 1 ppm oxygen. 1H,
31
P, and
13
C Nuclear Magnetic
Resonance (NMR) spectra were recorded on Bruker Avance 300 or Bruker Avance II 400 Ultrashield NMR spectrometers. Elemental analyses were performed at the London Metropolitan University. Substrates 5, 7, 9, 11, 13, 15, 18, 21 and products 6, 8, 10, 12, 14, 16, 19, 20, 22 and 23 have previously been described in the literature.1-3
Synthesis of [RuCl2(IPr*)(PPh3)(3-phenylindenylidene)](1): In the glovebox, M10 (1.00 g, 1.13 mmol) and IPr* (914 mg, 1.2 mmol)) were charged to a Schlenk flask and dissolved in toluene (3 mL). The reaction was taken out of the glovebox and stirred at 40 °C for 10 h under Ar. After this time, the mixture was allowed to cool to RT and the solvent was removed under vacuum. The remaining solid was recrystallised in a mixture of dichloromethane / pentane. The mixture was filtered, washed with cold methanol (2 x 5 mL) and cold hexane (8 x 25 mL), affording [RuCl2(IPr*)(PPh3)(3-phenylindenylidene)] (1) (750 mg, 0.49 mmol, 44%) as a microcrystalline solid. 1H NMR (C6D6, 400MHz): δ = 8.13 (d, J=7.3 Hz, 1 H), 7.67 - 8.00 (m, 7 H), 7.57 (t, J=7.8 Hz, 5 H), 6.55 - 7.42 (m, 60 H), 6.24 (s, 1 H), 6.03 (s, 1 H), 5.90 (s, 1 H), 4.93 (s, 1 H), 4.51 (s, 1 H), 2.05 (s, 2 H), 1.77 (s, 3 H) ppm, 13C NMR (CD2Cl2 ,75MHz): δ = 301.02, 185.1, 183.8, 146.9, 146.7, 145.7, 145.2, 144.1, 141.0, 138.2, 135,8, 135.0, 134.8,
Formatted: Font: (Default) Symbol, 12 pt, English (U.S.)
132.1, 131.6, 130.0, 129.3, 129.0, 128.6, 128.3, 128.1, 128.1, 126.5, 123.6, 116.7, 50.8, 50.4, 22.5, 21.9, ppm,
31
P NMR (162MHz, C6D6) = δ = 27.54 ppm Anal. Calcd for C103H85Cl2N2PRu C,
79.62; H, 5.51; N 1.80; Found: C, 79.77; H, 5.25; N, 1.73.
Synthesis of [RuCl2(IPr*)(Py)(3-phenylindenylidene)](2): In the glovebox, M10 (1.00 g, 1.13 mmol) and IPr* (914 mg, 1.2 mmol) were weighed to a Schlenk flask and dissolved in toluene (3 mL), taken out of the glovebox, connected to a Schlenk
Formatted: Font: (Default) Symbol, 12 pt, English (U.S.)
line and stirred at 40 °C for 10 h under Ar. Pyridine (0.45 mL) was then added by syringe, the resulting solution was left stirring for 0.5 h, after which time pentane was added (35 mL) and the reaction left stirring for another 0.5 h. The resulting suspension was then cooled to -40°C, filtered and recrystalsed from dichloromethane/pentane. The mixture was filtered, washed with cold methanol (1 x 10 mL) and cold hexane (3 x 10 mL) affording compound [RuCl2(IPr*)(Py)(3phenylindenylidene)](2) (940 mg, 0.69 mmol, 73% yield).1H NMR (CD2Cl2 ,400MHz): δ = 8.12
Formatted: Font: (Default) Symbol, 12 pt, English (U.S.)
(d, J=7.2 Hz, 1 H), 7.85 (br. s., 2 H), 7.77 (d, J=5.1 Hz, 2 H), 6.42 - 7.57 (m, 60 H), 6.31 (br. s., 2 H), 6.09 - 6.19 (m, 1 H), 5.95 (s, 1 H), 5.72 - 5.86 (m, 1 H), 5.69 (s, 1 H), 4.97 - 5.01 (m, 1 H), 4.93 (d, J=1.9 Hz, 1 H), 4.08 (d, J=1.7 Hz, 1 H), 2.24 (s, 3 H), 2.10 - 2.18 (m, 1 H), 1.22 ppm (s, 3 H) 13
C NMR (CD2Cl2 ,75MHz): δ = 153.6, 146.3, 143.1, 142.7, 142.0, 140.7, 140.2, 140.0, 139.8,
137.3, 136.5, 135.6, 133.8, 131.7, 130.7, 130.0, 129.3, 128.6, 128.0, 126.8, 126.4, 126.2, 124.6, 124.5, 123.9, 118.1, 22.7, 22.0, 20.8 ppm Anal. Calcd for C89H71Cl2N3Ru C, 78.86; H, 5.35; N 3.10; Found: C, 78.81; H, 5.16; N, 3.05.
Synthesis of [RuCl2(IPr)(PPh3)(3-phenylindenylidene)](3): In the glovebox, M10 (0.500 g, 0.56 mmol) and IPr (240 mg, 0.62 mmol) were charged to a Schlenk flask and dissolved in toluene (3 mL). The reaction was taken out of the glovebox, stirred at 40 °C for 4 h under Ar. After this time, the mixture was allowed to cool to RT and the solvent removed under vacuum. The remaining solid and recrystallised in a mixture of dichloromethane / pentane. The mixture was filtered, washed with cold methanol (2 x 5 mL) and cold hexane (8 x 25 mL), affording [RuCl2(IPr)(PPh3)(3-phenylindenylidene)] (3) (410 mg, 0.41 mmol, 81%) as a microcrystalline solid. Spectroscopic data for the product were in accordance with the literature.4 Anal. Calcd for C61H65Cl2N2PRu C, 71.19; H, 6.37; N, 2.72; Found: C, 71.52; H, 6.19; N, 2.62.
Synthesis of [RuCl2(IPr)(Py)(3-phenylindenylidene)](4): In the glovebox, M10 (1.00 g, 1.13 mmol) and IPr (480 mg, 1.2 mmol) were weighed to a Schlenk flask and dissolved in toluene (3 mL), taken out of the glovebox, connected to a Schlenk
Formatted: Font: (Default) Symbol, 12 pt, English (U.S.)
line and stirred at 40 °C for 4 h under Ar. Pyridine (0.45 mL) was then added by syringe, the resulting solution was left stirring for 0.5 h, after which time pentane was added (35 mL) and the reaction left stirring for another 0.5 h. The resulting suspension was then cooled to -40°C. Filtration and recrystalysation in dichloromethane/pentane. The mixture was filtered, washed with cold methanol (1 x 10 mL) and cold hexane (3 x 10 mL) affording compound [RuCl2(IPr*)(Py)(3phenylindenylidene)](2) (630 mg, 0.76 mmol, 66% yield). 1H NMR (400 MHz, C6D6) δ ppm = 0.66 - 0.94 (m, 4 H) 1.00 - 1.39 (m, 6 H) 1.52 - 1.91 (m, 5 H) 2.80 - 2.97 (m, 1 H) 3.12 - 3.23 (m, 1 H) 3.23 - 3.38 (m, 1 H) 4.63 - 4.81 (m, 1 H) 6.06 (t, J=6.92 Hz, 1 H) 6.31 - 6.42 (m, 2 H) 6.60 (s, 1 H) 6.64 - 6.75 (m, 1 H) 6.87 - 6.95 (m, 2 H) 7.02 - 7.13 (m, 1 H) 7.32 - 7.45 (m, 2 H) 7.74 (d, J=7.52 Hz, 1 H) 8.19 (d, J=5.12 Hz, 1 H) 8.67 (d, J=7.217 Hz, 1 H) ppm 13C NMR (75 MHz, CD2Cl2) δ ppm = 243.095, 25.202, 25.54-26.10, 26.545-26.91, 27.62, 28.94, 29.878, 30.106-30.72, 124.14, 1276.096, 127.767, 128.44, 129.19, 129.52, 130.81-131.56, 132.42, 132.54, 132.60-132.73, 137.24, 137.40, 140.04, 141.20, 141.878, 142.21, 145.71, 153.325, 181.656, 300.765 ppm Anal. Calcd for C48H55Cl2N3Ru C, 68.15; H, 6.55; N, 4.97; Found: C, 67.68; H, 6.72; N, 5.04.
General procedure for RCM and Enyne reactions: In a Radley carousel under argon or nitrogen, a reaction tube was charged with the substrate (0.25 mmol) and the solvent (2.5 mL) (CH2Cl2 for reaction at RT and 40 °C, toluene for reactions at 80 °C), then precatalyst (0.0025 mmol). The progress of the reaction was monitored by 1H NMR. Conversion determined by 1H NMR spectroscopy by integrating the characteristic signals for allylic proton resonances.
General procedure for CM reactions: In a Radley carousel under argon or nitrogen, a reaction tube was charged with one equivalent of the electron rich substrates (0.25 mmol) and two equivalents of the electron poor olefin (0.5 mmol) solvent (2.5 mL), then precatalyst (0.0025 mmol). The progress of the reaction was monitored by 1
H NMR. At reaction completion solvent was removed under vacuum and the crude residue was
checked by 1H NMR. Conversion determined by 1H NMR spectroscopy by integrating the characteristic signals for allylic proton resonances.
N
PhPh Cl
Ph Ru Cl
31
P NMR of complex 1 in C6D6:
6.0
5.5
5.0
4.5 0.776
6.5
0.764
7.0
0.748 0.880 0.774
7.5
63.484
8.0
5.838
8.5
7.146
9.0
1.000
9.5
4.0
1.772
Ph Ph
Ph
PPh3
3.5
3.0
2.5
2.0 ppm 3.158
Ph
N
2.506
Ph Ph
2.049
7.844 7.817 7.792 7.678 7.601 7.575 7.479 7.451 7.424 7.304 7.287 7.261 7.237 7.210 7.160 7.130 7.108 7.085 7.069 7.055 7.031 7.012 6.981 6.915 6.876 6.851 6.817 6.800 6.789 6.758 6.699 6.680 6.656 6.576 6.494 6.405 6.351 6.262 6.240 6.217 6.098 6.028 5.995 5.906 4.928 4.513
NMR data of [RuCl2(IPr*)(PPh3)(3-phenylindenylidene)] (1): 1 H NMR of complex 1 in C6D6:
27.344 Ph Ph Ph
N
Ph Ph
N
PhPh Cl
Ph
Ph
Ru Cl PPh3
120
100
90
80
70
60
50
40
30
20
10
0
-10
-20
-30
-40
-50
-60
ppm
1
145.391 141.815 139.844 139.363 135.560 135.317 135.244 135.171 135.001 131.506 131.223 130.940 130.627 130.336 130.168 129.776 129.425 129.376 129.327 128.826 128.471 128.409 128.346 127.763 127.146
C{ H}zz NMR of complex 1 in CD2Cl2 301.020
13
110
Ph Ph Ph
N
N
Ph Ph
PhPh Cl
Ph Ru
Ph
Cl PPh3
320
300
280
260
240
220
200
180
160
NMR data of [RuCl2(IPr*)(Py)(3-phenylindenylidene)] (2): 1
H NMR of complex 1 2 in CD2Cl2:
140
120
100
ppm
300 Ph Ph
Ph N
Ph N
250 PhPh Cl Ru
200 5.5 5.0
150 4.5
Ph
4.0
NMR data of [RuCl2(IPr)(PPh3)(3-phenylindenylidene)] (3): 1 H NMR of complex 1 3 in C6D6: N
PhPh Cl Ru
3.5
100 3.0 2.5
50
3.520
6.0
3.298
6.5 0.813
7.0
1.584
7.5 1.166
8.0
60.534
Ph
N
21.996 21.559 20.867
13 4.082
1.000
8.5
179.652 153.656 146.311 145.043 143.086 142.707 142.015 140.752 140.240 140.042 139.774 138.375 137.290 136.472 135.646 133.798 131.709 130.694 129.894 129.621 129.375 129.275 128.565 128.396 128.245 127.996 126.825 126.172 125.643 124.711 124.567 123.932 118.141
301.150
Ph Ph Ph Ph
Cl
Ph
N
2.0 1.5 ppm
C{1H} NMR of complex 21 in CD2Cl2:
Ph Ph
Cl Ph
N
ppm
1.218
2.245 2.144
7.433 7.412 7.393 7.321 7.305 7.287 7.264 7.244 7.184 7.166 7.125 7.105 7.088 7.043 7.025 7.006 6.975 6.958 6.942 6.925 6.908 6.891 6.871 6.797 6.744 6.730 6.667 6.556 6.308 6.152 5.948 5.815 5.687 4.978 4.929 4.925 4.082 4.078
29.897
31
120
110
100
90
80
70
60
7 6
50
40
5
30
20
4
N
10
0
NMR data of [RuCl2(IPr)(Py)(3-phenylindenylidene)] (4): 1 H NMR of complex 1 4 in C6D6:
-10
-20
2.703 5.631 3.372 3.422 3.231
Cl
1.697
Ru
0.933
0.797
5.946
8
17.631
9.176 3.254
9 2.939
1.000
N N
Cl Ph
PPh3
3 2
Ru Cl
-30
-40
-50
ppm
P NMR of complex 1 3 in C6D6:
N
Cl Ph
PPh3
ppm
8.048 8.024 7.704 7.681 7.676 7.429 7.426 7.420 7.404 7.397 7.392 7.370 7.364 7.262 7.237 7.053 7.045 7.034 7.022 7.008 7.003 6.997 6.984 6.978 6.966 6.961 6.955 6.944 6.938 6.920 6.913 6.897 6.890 6.863 6.775 6.681 6.645 6.585 6.580 1.667 1.645 1.475 1.454 1.418 1.396 1.161 1.138 1.065 1.042 0.988 0.964 0.943 0.875 0.851 0.816 0.793 0.788 0.765
300 N
Cl Ru Cl
250
200 4
150 3
100
2
50
6.847
5 10.381
Cl
9.174
Ru
0.929
0.952 0.924
6
0.962
7 2.028
8 2.079
3.372
4.370
2.344
2.035
1.000
9
181.406 153.093 149.329 147.008 145.559 142.051 141.628 141.045 139.881 137.241 137.089 136.326 135.520 132.470 132.389 132.259 131.199 130.844 129.693 129.359 129.034 128.808 128.279 127.519 126.812 126.340 125.109 124.141 123.988 123.705 117.522 30.290 29.628 28.790 27.464 26.544 25.639 24.863
13
300.492
N N
Cl Ph
N
1 ppm
C{1H} NMR of complex 1 4 in C6D6:
N
Ph
N
ppm
Formatted: Font: (Default) Times, 12 pt, Bold, Spanish (Venezuela)
REFERENCES
Formatted: Spanish (Venezuela)
(1) (2)
Formatted: Spanish (Venezuela)
(3) (4)
Clavier, H.; Nolan, S. P. Chem.—Eur. J. 2007, 13, 8029. Rix, D.; Caijo, F.; Laurent, I.; Boeda, F.; Clavier, H.; Nolan, S. P.; Mauduit, M. J. Org. Chem. 2008, 73, 4225. Boeda, F.; Bantreil, X.; Clavier, H.; Nolan, S. P. Adv. Synth. Catal. 2008, 350, 2959. Jafarpour, L.; Schanz, H.-J.; Stevens, E. D.; Nolan, S. P. Organometallics 1999, 18, 5416.
Field Code Changed
