Organometallics
Cl PRu: C, 64.78; H, 7.70; N, 4.72. Found: C, 65.04; H, 7.93;
CNH]Ru(CHPh)(py)Cl (9). A 100 mg (0.1123 mmol)
ARTICLE
C
48
H
68
N
3
2
program. The pulse sequence and the values collected for the construc-
tion of the Eyring plot of 3 can be found in the Supporting Information.
Eyring plot data for compounds 4, 5, and 1 were obtained from their
N, 4.89.
Mes
[
2
Mes
30
amount of
[CNH]Ru(CHPh)(PCy
3
)Cl
2
was dissolved in 10 mL
original source.
of toluene, and 1 mL of pyridine was added dropwise to the stirred
solution. A color change from maroon to green is observed upon stirring
for 10 min. The reaction was allowed to stir for 30 min total, at which
time the solution was concentrated and pentane was added to afford a
green suspension, which was cooled to À30 °C before filtration. The
green product was dried under vacuum. X-ray suitable crystals can be
General Procedures for RCM of S1. To a Teflon-sealed J. Young
NMR tube were added 1.650 μmol of Ru catalyst, 0.040 mL (0.1650
mmol) of diethyl diallylmalonate, and 0.60 mL of CD Cl . The sample
2 2
1
was then heated to 30 °C, and conversion was determined by H NMR
using the ratio of methylene signals of the product relative to the
substrate. Conversions of highly active catalysts are measured by
equilibrating the sample containing the dissolved catalyst to 30 °C in
the NMR probe before injection of the substrate via syringe.
grown via slow evaporation from a concentrated sample in methylene
1
chloride. Yield: 50 mg (73%). H NMR (400 MHz, CD
2
Cl
2
) δ: 2.04 (s,
3
6
6
1
2
H, ÀArCH ), 2.06 (s, 3H, ÀArCH ), 2.28 (s, 6H, ÀArCH ), 2.42 (s,
General Procedures for RCM of S2. Procedures are as described
for RCM of S1 using 0.021 mL (0.1650 mmol) of 1,6-heptadien-4-ol,
8.250 μmol of Ru catalyst, and 0.62 mL of CD Cl .
2 2
General Procedures for ROMP of S3. Procedures are as
described for RCM of S1 using 0.020 mL (0.1650 mmol) of 1,5-
cyclooctadiene, 0.10 mL of a 1.65 mM solution (0.1650 μmol) of Ru
3
3
3
H, ÀArCH ), 3.61 (m, 2H, ÀN CH ), 4.74 (m, 2H, ÀN CH ),
3
Mes
2
imid
2
.02 (t, 2H, J = 7.1 Hz, Àm-pyH), 6.17 (s, 1H, ÀimidH), 6.42 (s,
H, ÀimidH), 6.46 (br, 1H, Àp-pyH), 6.51 (s, 2H, ÀMesH), 6.57 (s,
H, ÀMesH), 6.95 (t, 2H, J = 7.1 Hz, Àm-PhH), 7.23 (sh, 1H, Àp-
PhH), 7.30 (br, 1H, ÀNH), 8.16 (d, 2H, J = 7.1 Hz, Ào-PhH), 8.50 (d,
13
2
H, J = 6.1 Hz, Ào-pyH), 19.8 (s, 1H, ÀRuCHPh). C NMR (151
MHz, CD Cl ), 51.19
) δ: 19.34, 20.81, 21.34, 21.53 (ÀArCH
catalyst in CD Cl , and 0.52 mL of CD Cl .
2 2 2 2
X-ray Crystallographic Analysis. All crystals were mounted on a
glass fiber and measured on a Bruker X8 diffractometer with graphite-
monochromated Mo KR radiation. The data were collected at a
temperature of À100.0 ( 0.1 °C with the Bruker APEX II CCD area
detector set at a distance of 36.00 mm. Data were collected and
2
2
3
(
(
(
(
ÀN CH ), 52.93 (ÀN CH ), 122.5 (Àm-pyC), 123.2, 124.0
Mes
2
imid
2
ÀimidC), 127.8, 129.6, 129.7, 130.5, 131.5, 131.6 (ÀArC), 132.5
ÀArCipso), 135.4 (Àp-pyC), 137.5, 137.7, 138.6, 145.1, 153.3
ÀArC ), 153.8 (Ào-pyC), 185.1 (ÀRuC
ipso
), 320.0 (ÀRuCHPh).
NCN
3
8
Anal. Calcd for C H N Cl Ru: C, 61.04; H, 5.85; N, 8.14. Found: C,
integrated using the Bruker SAINT software package and corrected
30
40
4
2
39
6
1.21; H, 5.96; N, 8.47.
for absorption effects using the multiscan technique (SADABS). The
data were corrected for Lorentz and polarization effects, and the
Mes
[
CNH]Ru(CHPh)(PMe )Cl (11). To a 10 mL toluene solution
3 2
4
0
Mes
structure was solved by direct methods. All non-hydrogen atoms were
refined anisotropically, while all hydrogen atoms except those coordi-
nated to the amino tether were placed in calculated positions but were
not refined. Amino protons were located in a difference map and refined
containing 110 mg (0.1597 mmol) of
was added 0.02 mL (0.1940 mmol) of PMe at room temperature. The
green mixture was allowed to stir for 1 h and tested for completion
periodically via unlocked P{ H} NMR. The solution was then con-
centrated, and hexanes was added to afford a dark green suspension. The
suspension was chilled to À35 °C before being filtered. The green
product was collected and washed with hexanes followed by drying
under vacuum. X-ray suitable crystals can be grown via slow evaporation
[CNH]Ru(CHPh)(py)Cl
2
3
31
1
41
isotropically. All refinements were performed using the SHELXTL
crystallographic software package of Bruker-AXS. Selected bond lengths
and angles of significant importance for 3, 9, and 11 are listed in Tables 1
and 5, respectively. For compound 9, atoms N03 and H3n were found to
be disordered and were modeled with their occupancies shared between
two positions (N03/N03(b) and H3n/H3n(b)) in a ratio of 2:1.
1
from a concentrated toluene solution. Yield: 74 mg (68%). H NMR
(
400 MHz, C
H, ÀArCH ), 2.15 (s, 9H, ÀArCH
H, ÀNMesCH
6
D
6
) δ: 0.78 (d, 9H, JHP = 8.8 Hz, ÀPCH
3
), 1.91 (s,
3
), 3.39 (m,
3
2
6
2
2
3
3
), 2.6 (s, 6H, ÀArCH
), 4.64 (m, 2H, ÀNimidCH
2
), 6.17 (s, 1H, ÀimidH),
’ ASSOCIATED CONTENT
2
.21 (br, 1H, ÀNH), 6.35 (br, 3H, imidH, ÀMesH), 6.78 (s,
H, ÀMesH), 7.02 (t, 2H, Àm-PhH), 7.24 (t, 1H, Àp-PhH), 8.29 (d,
S
Supporting Information. Details of the magnetization
b
13
H, J = 7.5 Hz, Ào-PhH), 20.0 (s, 1H, ÀRuCHPh). C NMR (151
transfer experiments for 3 (pulse sequence, stacked plot, plot of
MHz, CD Cl ) δ: 11.0 (d, J = 25 Hz, ÀP(CH ) ), 16.1, 17.7, 18.1,
normalized integrals, and the tabulated rate constants and T
1
2
2
CP
3 3
1
8.4 (ÀArCH
3
), 48.4 (ÀNMesCH
2
), 50.03 (ÀNimidCH
2
), 122.9, 123.1
values); table of RCM and ROMP results using 9 as a catalyst
precursor; crystallographic data for 3, 9, and 11 (CIF). This
material is available free of charge via the Internet at http://pubs.
acs.org.
(d, JCP = 3 Hz, imidC), 128.7, 128.8, 129.5, 129.6, 130.6 (ÀArC), 131.7,
1
32.0, 132.1, 136.9, 137.9, 138.5,147.0, 154.3 (ÀArCipso), 189.7 (d,
31 1
J
= 100 Hz, ÀRuC
), 311.0 (d, J = 127, ÀRuCHPh). P{ H}
CP
CP
NCN
NMR (162 MHz, C
C
N, 5.88.
6
D
6
) δ: À14.2 (s, ÀRu-PMe
3
). Anal. Calcd for
33
H
44
N
3
Cl PRu: C, 57.81; H, 6.47; N, 6.13. Found: C, 58.19; H, 6.78;
2
’
ACKNOWLEDGMENT
Magnetization Transfer. A sealable J. Young NMR tube was
charged with 17.0 mg (0.0191 mmol) of complex 3, 8.0 mg (0.0287
mmol) of PCy , and 0.6 mL of d10-o-xylene. The suspension was then
3
Funding for this research was provided by NSERC of Canada
in the form of a Discovery Grant to M.D.F.
allowed to thermally equilibrate at the experimental temperature, at
which point the contents will have completely dissolved (minimum
’
REFERENCES
(
1) Samojlowicz, C.; Bieniek, M.; Grela, K. Chem. Rev. 2009,
3
temperature of 80 °C required). The free PCy resonance was selectively
109, 3708.
inverted via a 180° Gaussian 1.1000 shaped pulse with a duration of
(
2) Acherrmann, L.; F €u rstner, A.; Weskamp, T.; Kohl, F. J.; Herrmann,
p22:50 ms at power level sp2. Twenty-one progressive mixing times
W. A. Tetrahedron Lett. 1999, 40, 4787.
3) Huang, J.; Stevens, E. D.; Nolan, S. P.; Petersen, J. L. J. Am. Chem.
Soc. 1999, 121, 2674.
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1, 953.
(5) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am.
Chem. Soc. 2000, 122, 8168.
ranging from 0.000003 to 30 s were run, and a subsequent nonselective
(
1
9
1
0° pulse was applied to record the FID. H decoupling with WALTZ-
6 was applied during the 90° pulse. Signal integrals of both the
(
coordinated and free PCy were analyzed with the CIFIT software to
3
1
obtain phosphine exchange rate constants. Standard T recovery experi-
ments were performed at each temperature and analyzed with the CIFIT
2
340
dx.doi.org/10.1021/om2000844 |Organometallics 2011, 30, 2333–2341