Organometallics
ARTICLE
Isopropyl(20,40,60-triisopropyl-3-vinylbiphenyl-4-yl)sulfide (13). 13
was prepared by the same procedure as 8, starting from 12 (yield 0.43
g, 81%). 1H NMR (200 MHz, CDCl3, ppm): δ 1.11 (d, J = 7.0 Hz, 12H),
1.33 (d, J = 7.0 Hz, 6H), 1.34 (d, J = 6.8 Hz, 6H), 2.65 (sept, J = 7.0 Hz,
2H), 2.96 (sept, J = 7.0 Hz, 1H), 3.38 (sept, J = 6.8 Hz, 1H), 5.31 (dd, J =
11.0 Hz, J = 1.2 Hz, 1H), 5.62 (dd, J = 17.4 Hz, J = 1.2 Hz, 1H), 7.04-
7.08 (m, 3H), 7.33-7.49 (m, 3H). 13C NMR (50 MHz, CDCl3, ppm): δ
23.2, 24.0, 24.2, 30.2, 34.2, 38.5, 115.3, 120.5, 127.2, 129.4, 131.9, 132.8,
135.2, 136.3, 139.3, 139.9, 146.4, 148.0. C26H36S MS (EI): m/z found
380.3 (Mþ), 337.3 (Mþ - iPr), calcd 380.2.
General Procedure for cis-Dichloro Catalysts (4-6). Styrene
(9, 10, 13) (0.14 mmol), cuprous chloride (0.17 mmol), and second-
generation Grubbs catalyst 1b (0.14 mmol) were dissolved in 6 mL of
dichloromethane in a 10 mL round-bottomed flask under dry nitrogen
topped with a reflux condenser. The reaction mixture was refluxed for 24
h. The resulting mixture was concentrated to 2-3 mL of DCM. The
crude product was purified by chromatography on silica gel using 7:3 n-
hexane/acetone as eluent.
4cis: dark green solid (55.0 mg, 54%). Crystals suitable for X-ray
analysis were obtained by laying hexanes over a solution of 4cis in
dichloromethane and hexanes for few days at -18 °C. 1H NMR (500
MHz, CD2Cl2, ppm): δ 0.84 (d, J = 7.0 Hz, 3H), 1.43 (d, J = 7.0 Hz, 3H),
1.55 (s, 1H), 1.69 (s, 1H), 2.37 (s, 1H), 2.46 (s, 1H), 2.58 (s, 1H), 2.65
(s, 1H), 3.6 (sept, J = 7.0 Hz, 1H), 3.75-3.88 (m, 2H), 3.97-4.04 (m,
1H), 4.08-4.14 (m, 1H), 6.02 (s, 1H), 6.83 (s, 1H), 7.03-7.04 (m,
2H), 7.13 (s, 1H), 7.38-7.41 (m, 1H), 7.49 (t, J = 8.0 Hz, 2H), 7.54 (d, J
= 8.0 Hz, 1H), 7.59-7.61 (m, 2H), 7.76 (dd, J = 2.0 Hz, J = 8.0 Hz, 1H),
17.24 (s, 1H). 13C NMR (125 MHz, CD2Cl2, ppm): δ 17.7, 18.9, 19.8,
20.4, 20.6, 21.3, 24.3, 26.3, 39.3, 51.4, 51.8, 122.2, 126.7, 127.4, 128.5,
129.2, 129.4, 129.7, 130.0, 130.8, 131.2, 131.7, 133.9, 135.5, 136.0, 137.4,
137.9, 138.8, 139.3, 139.4, 140.3, 140.6, 143.3, 157.3, 213.5, 285.6. FAB-
MS: calcd for C37H42Cl2NRuS [M]þ 718.1; found 718.1. C46H60-
1.17 (s, 3H), 1.22 (d, J = 7.5 Hz, 3H), 1.3 (d, J = 6.5 Hz, 6H), 1.37 (d, J =
7.5 Hz, 3H), 1.42 (d, J = 6.5 Hz, 3H), 2.15 (s, 3H), 2.38 (s, 3H), 2.51 (s,
3H), 2.61 (s, 3H), 2.84 (s, 3H), 2.91-2.98 (m, 2H), 3.26 (sept, J = 7.5
Hz, 1H), 3.78-3.86 (m, 1H), 3.93-4.03 (m, 2H), 4.14-4.21 (m, 1H),
6.42 (s, 1H), 6.93 (s, 1H), 6.98 (s, 1H), 7.05-7.06 (m, 2H), 7.14 (m,
2H), 7.34 (dd, J = 2.0 Hz, J = 7.0 Hz, 1H), 7.53 (d, J = 7.0 Hz, 1H), 16.18
(s, 1H). 13C NMR (125 MHz, CD2Cl2, ppm): δ 16.9, 19.3, 19.4, 19.7,
20.7, 20.8, 20.9, 23.5, 23.7, 23.8, 23.9, 24.0, 25.2, 30.0, 31.0, 31.5, 34.4,
38.9, 51.2, 51.5, 120.6, 120.9, 125.3, 128.2, 129.7, 129.8, 129.9, 130.3,
130.7, 132.7, 134.7, 135.1, 135.2, 135.4, 136.1, 138.0, 138.1, 138.9, 139.9,
142.9, 146.0, 147.2, 148.7, 156.5, 212.0, 285.2. FAB-MS: calcd for
C46H60Cl2NRuS[M]þ 844.29; found 844.3. C46H60Cl2N2RuS 2CH2Cl2,
3
M = 929.93, orthorhombic, space group Pbca, a = 16.3458(2) Å, b =
16.3996(2) Å, c = 34.2389(5) Å, β = 90.0(0)°, V = 9178.2(2) Å3, Z = 8, T
= 110(2) K, Fcalcd = 1.346 g cm-3, μ(Mo KR) = 0.654 mm-1, 24 631
reflections measured (2θmax = 51.0°), 10 455 unique (Rint = 0.052), final
R = 0.0506 (wR = 0.1224) for 7200 reflections with I > 2σ(I) and R =
0.086 (wR = 0.140) for all data, Δ|Fmax| = 1.39 e/Å3. The asymmetric
unit contains three additional molecules of a dichloromethane solvent,
two ordered and one that could not be modeled reliably by discrete
atoms and was excluded from the final crystallographic refinement.
General Procedure for trans-Dichloro Catalysts (4-6). Trans iso-
mers were synthesized according to the same procedure as the cis
isomers by shortening reaction time (2 h) and lowering temperature
(room temperature).
4trans: green solid (30 mg, 30%). 1H NMR (500 MHz, CD2Cl2): δ
0.95 (d, J = 7.0 Hz, 6H), 2.39 (s, 6H), 2.47 (s, 12H), 3.08 (sept, J = 7.0
Hz, 1H), 4.14 (s, 4H), 6.98 (s, 1H), 7.06 (s, 4H), 7.39 (t, J = 7.5 Hz, 1H),
7.47-7.50 (m, 3H), 7.53-7.55 (m, 2H), 7.77-7.79 (m, 1H), 17.24 (s,
1H).
5trans: green solid (40 mg, 39%). 1H NMR (500 MHz, CD2Cl2, ppm): δ
1.00(d,J= 7.0 Hz, 6H), 1.26 (s, 12H), 2.25 (s, 6H), 2.46 (s, 12H), 3.10 (sept,
J = 7.0 Hz, 1H), 4.12 (s, 4H), 6.54 (s, 1H), 6.99 (4H), 7.11-7.18 (m, 3H),
5.35 (dd, J = 2.0 Hz, J = 7.5 Hz, 1H), 7.53 (d, J = 7.5 Hz, 1H), 17.20 (s, 1H).
6trans: green solid (43 mg, 37%). 1H NMR (500 MHz, CD2Cl2, ppm):
δ 1.00-1.05 (m, 12H), 1.29 (d, J = 7.0 Hz, 12H), 2.22 (s, 6H), 2.45-2.58
(m, 14H), 2.94 (sept, J = 7.0 Hz, 1H), 3.14 (sept, J = 7.0 Hz, 1H), 4.11 (s,
4H), 6.55 (d, J = 2.0 Hz, 1H), 6.97 (s, 4H), 7.07 (s, 2H), 7.33 (dd, J = 2.0
Hz, J = 8.0 Hz, 1H), 7.50 (d, (d, J = 8.0 Hz, 1H), 17.22 (s, 1H).
Alternative Procedure for trans-Dichloro Complexes.
Trans isomers can also be synthesized according to the same procedure
as the cis isomers by replacing the reaction solvent with benzene and
lowering the temperature (room temperature).
Cl2N2RuS CH2Cl2, M = 929.93, monoclinic, space group P21/c, a =
3
13.2232(2) Å, b = 7.9543(1) Å, c = 32.1113(6) Å, β = 101.5323(7)°, V =
3309.32(9) Å3, Z = 4, T = 110(2) K, Fcalcd = 1.443 g cm-3, μ(Mo KR) =
0.728 mm-1, 16 584 reflections measured (2θmax = 51.0°), 7741 unique
(Rint = 0.038), final R = 0.0495 (wR = 0.1239) for 5551 reflections with I
> 2σ(I) and R = 0.079 (wR = 0.141) for all data, Δ|Fmax| = 2.09 e/Å3.
5cis: dark green solid (51.0 mg, 49%). Crystals suitable for X-ray
analysis were obtained by laying hexanes over a solution of 5cis in
dichloromethane and hexanes for few days at -18 °C. 1H NMR (500
MHz, CD2Cl2, ppm): δ 0.88 (d, J = 6.5 Hz, 3H), 1.41 (s, 3H), 1.87 (s,
3H), 1.99 (s, 3H), 2.36 (s, 3H), 2.38 (s, 3H), 2.54 (s, 3H), 2.57 (s, 3H),
2.75 (s, 3H), 3.48 (sept, J = 6.5 Hz, 1H), 3.78-3.85 (m, 1H), 3.91-4.04
(m, 2H), 4.13-4.19 (m, 1H), 6.32 (s, 1H), 6.74 (s, 1H), 6.90 (s, 1H),
7.06-7.18 (m, 5H), 7.33-7.35 (m, 1H), 7.56 (d, J = 8.0 Hz, 1H), 16.94
(s, 1H). 13C NMR (125 MHz, CD2Cl2, ppm): δ 17.4, 19.3, 19.7, 20.2,
20.8, 21.0, 21.2, 21.3, 21.5, 24.5, 39.3, 51.4, 51.5, 125.5, 127.9, 128.1,
128.9, 129.9, 130.1, 130.4, 130.9, 132.3, 134.8, 135.6, 135.8, 135.9, 136.8,
137.0, 138.4, 139.9, 140.5, 143.2, 156.8, 213.5, 285.4. FAB-MS: calcd for
C39H46Cl2NRuS [M]þ 746.1; found 746.1. C39H46Cl2N2RuS, M =
746.81, monoclinic, space group P21/n, a = 15.7063(7) Å, b =
15.3923(9) Å, c = 19.8339(12) Å, β = 112.494(3)°, V = 4430.2(4) Å3,
3trans. 1-(Isopropylsulfanyl)-2-vinylbenzene (0.065 mmol), cuprous
chloride (0.065 mmol), and second-generation Grubbs catalyst 1b (0.06
mmol) were dissolved in 6 mL of benzene in a 10 mL round-bottomed
flask under dry nitrogen. The reaction mixture was stirred at room
temperature for 24 h. The resulting mixture was purified by chroma-
tography on silica gel using 7:2 n-hexane/acetone as eluent.
3trans: green solid (31.5 mg, 85%).
General Procedure for Isomerization Rate Study. A
0.5 μmol amount of complex was weighed in a vial. In a glovebox,
deuterated solvent was added (0.5 mL) followed by the additive (if
necessary). The solution was transferred to a screw-cap NMR tube and
closed tight. Reaction progress was monitored by 1H NMR.
General Procedure for RCM Reactions. A round-bottom flask
was charged with precatalyst (2 μmol), olefin (0.2 mmol, 0.1 M), and
toluene (2 mL). The reaction mixture was stirred at room temperature
(for trans catalysts) or 80 °C (cis catalysts). Reaction progress was
monitored by GC-MS.
Z = 4, T = 110(2) K, Fcalcd = 1.120 g cm-3, μ(Mo KR) = 0.546 mm-1
25 141 reflections measured (2θmax = 51.0°), 8043 unique (Rint
,
=
0.093), final R = 0.0633 (wR = 0.1561) for 4191 reflections with I >
2σ(I) and R = 0.125 (wR = 0.181) for all data, Δ|Fmax| = 0.67 e/Å3. The
asymmetric unit contains two additional molecules of a severely disordered
dichloromethane solvent, which could not be modeled reliably by discrete
atoms and were excluded from the final crystallographic refinement.
6cis: dark green solid (75.0 mg, 63%). Crystals suitable for X-ray
analysis were obtained by laying hexanes over a solution of 6cis in
dichloromethane and hexanes for few days at -18 °C. 1H NMR (500
MHz, CD2Cl2, ppm): δ 0.83-0.86 (m, 6H), 1.00 (d, J = 7.5 Hz, 3H),
General Procedure for ROMP Reactions. A round-bottom
flask was charged with initiator (3.33 μmol, 0.3%), olefin (1 mmol),
mesitylene (internal standard, 200 mg), and toluene (2 mL). The
reaction mixture was stirred at room temperature (for trans catalysts)
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dx.doi.org/10.1021/om1011402 |Organometallics 2011, 30, 1607–1615