124 Organometallics, Vol. 29, No. 1, 2010
Szadkowska et al.
0.1 mol % of either of the introduced catalysts accomplished
complete RCM of diethylallyl(2-methylallyl)malonate at
110 °C in less than 48 h. Although the reaction time is not
particularly impressive, the results are good indications of
the high temperature stability of the compounds under
investigation. The latency of complex IX, containing the
π-conjugated system, was more pronounced than that of the
more “flexible” counterpart VIII, as revealed by determina-
tion of the “switching temperatures” for initiators VIII and
IX in ROMP of several norbornene derivatives. Both dor-
mant catalysts/initiators could be useful in a range of high-
temperature applications.
Synthesis of Catalyst IX, (SPY-5-31)-Dichloro-(κ2(C,N)-
2-(benzo[h]quinolin-10-yl)methylidene)(1,3-bis(2,4,6-trimethyl-
phenyl)4,5-dihydroimidazol-2-ylidene)ruthenium . A Schlenk
tube equipped with a stirring bar was charged with (H2IMes)-
(PCy3)Cl2RudCHPh (Gru-III0) (622.0 mg, 0.733 mmol) and 10
(166.2 mg, 0.822 mmol). The tube was flushed with argon, and
anhydrous CH2Cl2 (25 mL) was added. The purple reaction
mixture was stirred at 25 °C for 48 h, whereupon the color
changed to dark green. The volume of the solvent was reduced to
about 5 mL, and upon addition of Et2O (50 mL) a green
precipitate formed, which was filtered off. The residue was
washed with Et2O (3 ꢀ 10 mL) and dried in vacuo. Yield:
282.1 mg (57%).
1H NMR (δ, 20 °C, 500 MHz, CDCl3): 19.19 (s, 1H,
3
3
RudCH), 8.25 (d, JHH = 5.0 Hz, 1H, bq2), 8.17 (d, JHH
=
Experimental Section25
7.5 Hz,1H, bq7), 8.07 (d, 3JHH = 8.0 Hz,1H, bq4), 7.90 (d, 1H,
bq5), 7.64 (m, 2H, bq6,8), 7.44 (dd, 3JHH = 8.0 Hz, 3JHH = 5.0
Hz, 1H, bq3), 7.17 (s, 4H, PhMes3,5), 7.10 (d, 3JHH = 7.5 Hz, 1H,
bq9), 4.20 (s, 4H, NCH2), 2.55 (bs, 12H, CH3), 2.50 (s, 6H, CH3).
13C NMR (δ, 20 °C, 125 MHz, CDCl3): 290.4 (1C, RudCH),
215.5 (1C, NCN), 147.7 (1C, bq2), 146.0 (1C, bq10b), 142.8, 139.4
(b), 138.8, 137.1, 136.1, 129.9, 129.8, 129.7, 128.6, 126.9, 124.9,
122.7, 121.6 (23C, bq3-10a, PhMes1-6), 51.7 (b, 2C, NCH2), 21.4
(2C, CH3), 19.5 (b, 4C, CH3). MS (FD/FI, m/z): calcd for [M]þ•
(C35 H35N335Cl2102Ru) 669.1252; found 669.1274. IR (KBr): ν
2951, 2916, 2855, 2737, 1739, 1622, 1607, 1581, 1516, 1481, 1431,
1419, 1402, 1379, 1336, 1314, 1292, 1261, 1213, 1185, 1170, 1135,
1034, 993, 976, 914, 882, 855, 839, 794, 759, 713, 643, 615, 578,
506, 458, 422, 411 cm-1. Anal. Calcd for C35H35N335Cl2102Ru:
C, 62.82; N, 6.27; H, 5.27; Cl, 10.58. Found: C, 63.00; N, 6.12; H,
5.43; Cl, 10.47.
General Syntheses of Catalysts. Synthesis of Catalyst VIII,
SPY-5-31)-Dichloro-(κ2(C,N)-N-2-(2-vinylbenzylidene)pyridine-
(1,3-bis(2,4,6-trimethylphenyl)4,5-dihydroimidazol-2-ylidene)-
ruthenium. To a solution of 4 (140 mg, 0.77 mmol) in CH2Cl2
(5 mL) was added (H2IMes)(pyridine)2Cl2RudCHPh (Gru-III0)
(280 mg, 0.33 mmol), and the reaction mixture was stirred at
25 °C for 17 h. Afterward the mixture was evaporated to dryness
and the residue was redissolved in CH2Cl2/Et2O. Upon addition
of n-heptane a green precipitate formed, which was separated by
filtration, washed with heptanes, and dried under vacuum.
Yield: 109 mg (52%).
1H NMR (500 MHz, CDCl3): δ 2.45-2.49 (m, 18H), 4.15 (m,
4H), 6.65 (d, 1H), 7.10-7.16 (m, 4H), 7.55 (t, 1H), 7.57 (t, 1H),
7.60 (m, 2H), 7.74 (t, 1H), 7.97 (d, 1H), 8.14 (d, 1H), 16.85 (s,
1H). 13C NMR (125 MHz, CDCl3): δ 19.4, 19.4, 21.0, 21.1, 26.0,
26.2, 26.7, 26.8, 31.4, 121.9, 122.1, 122.7, 126.3, 128.0, 128.2,
128.5, 128.7, 129.4, 130.0, 130.1, 130.2, 135.0, 136.7, 138.4,
140.4, 145.0, 148.2, 156.5, 216.5, 314.4. MS (FD/FI, m/z): calcd
for [M]þ• (C33H35N335Cl2102Ru) 646.1330; found 646.1346. IR
(KBr): ν 3502, 2950, 2914, 2857, 2735, 1955, 1730, 1630, 1600,
1556, 1479, 1438, 1419, 1380, 1307, 1262, 1159, 1121, 1099, 1033,
950, 851, 789, 754, 735, 677, 641, 630, 579, 503, 474, 451, 420
cm-1. Anal. Calcd for C33H35N335Cl2102Ru: C, 61.29; N, 6.49;
H, 5.61; Cl, 10.95. Found: C, 61.17; N, 6.42; H, 5.61; Cl, 11.06.
Alternative Synthesis of Catalyst VIII. A Schlenk tube
equipped with a stirring bar was charged with ruthenium
complex (Ind-II) (127 mg, 0.15 mmol) and CuCl (17.8 mg, 0.18
mmol). The tube was flushed with argon and charged with
anhydrous methylene chloride (3.5 mL). Next, a solution of 7
(32 mg, 0.18 mmol) in methylene chloride (4 mL) was added
under an argon atmosphere, and the resulting solution was
stirred at 40 °C for 0.5 h. After this time, TLC indicated
complete conversion of the substrate. The resulting mixture
was concentrated in vacuo, the residue was redissolved in
AcOEt, and the solution was passed through a Paster pipet
containing a small amount of cotton and evaporated to dryness.
The crude product was purified by column chromatography
(using eluents cyclohexane/ethyl acetate, 10:1 to 1:1 v/v). After
evaporation of the solvents, the resulting solid was collected and
washed a few times with AcOEt and with cold n-pentane.
Acknowledgment. This work was supported by grant
number N204157636, which was provided by the
Polish Ministry of Science and Higher Education. K.G.
and K.W. thank the Foundation for Polish Science for
the “Mistrz” professorships. Single-crystal X-ray mea-
surements were accomplished at the Structural Research
Lab (SRL) of the Chemistry Department, Warsaw Uni-
versity, Poland. SRL has been established with finan-
cial support from European Regional Development
Fund in the Sector Operational Program “Improvement
of the Competitiveness of Enterprises, years 2004-2006”
project no. WKP_ 1/1.4.3./1/2004 /72/72/165/2005/U.
Parts of this work were supported by the Polymer Com-
petence Center Leoben GmbH (PCCL, Austria) within
the framework of the Kplus-Program of the Austrian
Ministry of Traffic, Innovation and Technology
(project II 2.2). K.G. and C.S. thank the European
Community for generous support, which was provided
through the Seventh Framework Program (grant no. CP-
FP 211468-2 EUMET).
Supporting Information Available: Complete characterization
of all new compounds, catalytic procedures, X-ray crystallo-
graphic tables, and data in CIF format. This information is
(25) For full experimental details and other information see the
Supporting Information.