1944 Organometallics, Vol. 25, No. 8, 2006
Monfette and Fogg
5 min. Stirring was continued for 20 min, after which the product
was collected by filtration, washed with diethyl ether (10 mL), and
dried in vacuo. Yield: 1.61 g (91%).
4JHH ) 1.6 Hz, 2H, py, o-CH), 7.45 (t of t, 3JHH ) 7.8 Hz, 4JHH
)
3
1.6 Hz, 1H, py, p-CH), 7.28 (d, JHH ) 7.0 Hz, 2H, Ph, o-CH),
3
7.17 (t, JHH ) 7.5 Hz, 1H, Ph, p-CH), 7.08 (s, 2H, IMes dCH),
Ru[K2-OSO2-2-O-C6H2(3,5-Cl2)](IMes)(py)(dCHPh), 5. A so-
lution of 2 (299 mg, 0.41 mmol) in 5 mL of benzene was added to
a rapidly stirred suspension of [C6H2(3,5-Cl2)(2-OTl)(SO3Na)] (193
mg, 0.41 mmol) in 5 mL of H2O. The mixture was stirred vigorously
for 2 h, over which time a green-blue suspension formed. This
material was filtered off and washed with ether (10 mL), then
redissolved in 10 mL of THF and filtered through Celite to remove
TlCl. Concentration, addition of hexanes, and cooling to -35 °C
precipitated a blue-green powder, which was filtered off and dried
under vacuum. Yield: 242 mg (72%). 1H NMR (C6D6, 298 K): δ
17.68 (s, 1H, RudCH), 8.46 (d, 3JHH ) 5 Hz, 2H, py o-CH), 8.14
(d, 4JHH ) 3 Hz, 1H, Ar, aryloxide CH), 7.83 (d, 3JHH ) 7 Hz, 2H,
6.96-6.85 (m, 6H, Ph, m-CH; py, m-CH; Ar, Mes CH), 6.71 (d of
d, 3JHH ) 7.0 Hz, 4JHH ) 2.0 Hz, 1H, Ar, catechol o-CH), 6.70 (d
3
4
of d, JHH ) 7.0, JHH) 2.0 Hz, 1H, Ar, catechol o-CH), 6.58 (br
3
4
s, 2H, Mes CH), 6.49 (t of d, JHH ) 7.0 Hz, JHH ) 2.0 Hz, 1H,
3
4
Ar, catechol m-CH), 6.36 (t of d, JHH ) 7.0 Hz, JHH ) 2.0 Hz,
1H, Ar, catechol m-CH), 2.22 (s, 6H, Mes p-CH3), 2.16 (s, 6H,
Mes o-CH3), 1.88 (s, 6H, Mes o-CH3). 13C{1H} NMR (CDCl3, 298
K): δ 287.42 (RudCH), 189.60 (IMes NCN), 164.09 (Ar, catechol
O-C), 160.51 (Ar, catechol O-C), 154.68 (py, o-CH), 152.56 (Ph
Ci), 138.99 (Ar, Mes p-CMe), 136.58 (Ar, Mes o-CMe), 135.62
(Ar, Mes o-CMe), 135.14 (Ar, Mes Ci), 134.03 (py p-CH), 129.13
(Ar, Mes m-CH), 128.00 (Ph m-CH), 127.73 (Ph o-CH), 126.48
(Ph p-CH), 124.02 (IMes dCH), 123.70 (py, m-CH), 116.13 (Ar,
catechol CH), 114.77 (Ar, catechol CH), 114.17 (Ar, catechol CH),
113.76 (Ar, catechol CH), 21.06 (Mes p-CCH3), 17.82 (Mes
o-CCH3), 17.69 (Mes o-CCH3). Anal. Calcd for C39H39N3O2Ru:
C, 68.60; H, 5.76; N, 6.15. Found C, 69.03; H, 5.38; N, 6.14.
MALDI-TOF MS, m/z: calcd for [M - py]+• 604.2; found, 604.1.
General Procedure for Ring-Closing Metathesis. In a typical
experiment, 6 (10 mg, 14.6 µmol) and diethyl diallylmalonate (38.5
mg, 0.16 mmol) were weighed into separate vials. The catalyst was
dissolved in 1.00 mL of CDCl3, and 54.7 µL of this stock solution
was added to a solution of the substrate in 1.6 mL of solvent (final
[S] ) 100 mM). The reaction was divided between two sealed vials
and heated to reflux in a pierced aluminum block. Each experiment
was carried out in duplicate (total 4 runs), measuring conversions
by GC and NMR analysis.
4
Ph, o-CH), 7.53 (d, JHH ) 3 Hz, 1H, Ar, aryloxide CH), 7.23 (t,
3JHH ) 7 Hz, 1H, Ph, p-CH), 6.99 (t, 3JHH ) 8 Hz, 2H, Ph, m-CH),
6.77 (s, 2H, Ar, Mes CH), 6.60 (s, 2H, Ar, Mes CH), 6.49 (t, 3JHH
) 8 Hz, 1H, py, p-CH), 6.12 (t, 3JHH ) 7 Hz, 2H, py, m-CH), 6.06
(s, 2H, IMes dCH), 2.13 (s, 6H, Mes p-CH3), 1.99 (s, 6H, Mes
o-CH3), 1.66 (s, 6H, Mes o-CH3). 13C NMR signals could not be
directly observed, as the solubility of the complex in C6D6 is very
low, but the majority of the signals could be located via HMQC
and HMBC experiments (see text). 13C NMR (C6D6, 298 K): δ
320.9 (RudCH), 182.0 (IMes NCN), 154.0 (py, o-CH), 152.5 (Ph
Ci), 139.4 (Ar, Mes p-CMe), 136.0 (Ar, Mes Ci), 135.0 (py, p-CH),
132.5 (Ar, aryloxide CH) 130.9 (Ph o-CH), 129.6 (Ar, Mes CH),
129.3 (Ar, Mes CH), 128.3 (Ph, m-CH), 128.1 (Ph, p-CH), 126.0
(Ar, phenoxide CH), 124.6 (Ar, IMes dCH), 123.9 (py, m-CH),
20.8 (Mes, o-CH3), 17.8 (Mes, p-CH3). Anal. Calcd for C39H37-
Cl2N3O4RuS: C, 57.42; H, 4.57; N, 5.15. Found C, 57.77; H, 4.17;
N, 4.92. IR (KBr): ν(SdO) 1262 cm-1. MALDI-TOF MS, m/z:
calcd for [M - py]+• 736.1; found, 736.2.
Acknowledgment. This work was supported by the Natural
Sciences and Engineering Research Council of Canada, the
Canada Foundation for Innovation, the Ontario Innovation Trust,
and the Ontario Research and Development Corporation. Dr.
Melanie Eelman is thanked for carrying out the inert-atmosphere
MALDI MS analyses.
Ru(K2-O2C6H4)(IMes)(py)(dCHPh), 6. A solution of 2 (300
mg, 0.41 mmol) in 20 mL of benzene was treated with solid Tl2-
(o-O2C6H4) (216 mg, 0.42 mmol) and stirred vigorously for 2 h,
over which time it turned brown from green. The mixture was then
filtered through Celite to remove TlCl, and the filtrate was stripped
off to give a green solid, which was taken up in hexanes. The
suspension was chilled at -35 °C, and the solid was collected by
filtration, washed with diethyl ether (10 mL) and hexanes (5 × 10
mL), then dried in vacuo. Yield: 218 mg (77%). 1H NMR (CDCl3,
Supporting Information Available: 1H, 1H-13C HMQC, and
1
1H-13C HMBC NMR spectra for 5; H and 13C NMR spectra of
6. This material is available free of charge via the Internet at
3
298 K): δ 16.99 (s, 1H, RudCH), 8.36 (d of d, JHH ) 6.6 Hz,
OM050952J