Pyridyl-substituted indenyl ruthenium complexes: Synthesis, structures, and reactivities

Article abstract of DOI:10.1021/om100556y

We have investigated the synthesis of a novel pyridyl-substituted indenyl trinuclear ruthenium complex, {μ₂-η⁵: η¹-(C₅H₄N)(C₉H ₅)}Ru₃(CO)₉ (1), and its reactivities with pyridine derivatives, PPh₃, and different types of alkenes. Complex 1 was synthesized in 89% yield from Ru₃(CO)₁₂ and 3-(2-pyridyl)indene (1:1 mol ratio) in refluxing heptane. The reaction of 1 with a 5-fold excess of 3-(2-pyridyl)indene gave two complexes, {η¹- (C₅H₄N)(C₉H₆)}₂Ru(CO) ₂ (2) and {η⁵-(C₅H₄N)(C ₉H₆)}{η¹-(C₅H ₄N)(C₉H₆)}Ru₂(CO)₄ (3). Both were also converted back to 1 in the presence of an equimolar amount of Ru₃(CO)₁₂, although the yields were low. Reaction of 1 in refluxing toluene afforded an unexpected complex, {μ₃- η⁶:η³:η¹-(C₅H ₄N)(C₉H₅)}Ru₃(CO)₇ (4), via the loss of two CO groups. Complex 4 represents a completely new type of coordination mode (μ₃-η⁶:η³: η¹) of indenyl ligands in transition metal complexes. The reactions of 1 with 2-(2-pyridyl)indene, 1,2,3,5-tetramethyl-4-(2-pyridyl) cyclopentadiene, 1,2-diphenyl-4-(2-pyridyl)cyclopentadiene, and 2-phenylpyridine in refluxing heptane afforded the mono-and/or dinuclear complexes 5-9 via the cleavage of either a Ru-C(η¹) or Ru-C(η⁵) bond or both. In the case of PPh₃, only one of three carbonyls at the pyridyl-coordinated ruthenium center of 1 was replaced by PPh₃ to produce {μ₂-η⁵:η¹-(C ₅H₄N)(C₉H₅)}Ru₃(CO) ₈(PPh₃) (10). The reactions of 1 with various terminal alkenes (CH₂=CHR) gave only the dinuclear ruthenium complexes {? ⁵-(C₅H₄N)(C₉H₅CHCH ₂R)}Ru₂(CO)₅ (11-13, 15, and 17) via the insertion of alkenes into the Ru-C(η¹) bond of 1 with the exception of 2-vinylpyridine and CH₂=CHOCH₂CH₃, which reacted with 1 to yield the pyridyl-substituted complex {η⁵-(C₅H₄N)(C₉H ₅CHCH₂(C₅H₄N))}Ru ₂(CO)₄ (14) and two unexpected complexes, 13 and {η⁵-(C₅H₄N)(C₉H ₄CHCH₂CH₂CH(OCH₂CH ₃))}Ru₂(CO)₅ (18a and 18b), respectively. Complex 15 was also transformed to {η⁵-(C₅H ₄N)(C₉H₅CHCH₂CO₂CH ₃)}Ru₂(CO)₃(η⁵-CH ₂=CHCO₂CH₃) (16) in the presence of methyl acrylate. The reactions of 1 with internal alkenes such as norbornene and cyclohexene gave complexes 19-22 in very low yields also via the insertion of alkenes into the Ru-C(η¹) bond of 1, with the concomitant formation of a small amount of 4. The molecular structures of 1-5, 8-11, 13-16, 18a, 18b, and 21 were determined by X-ray diffraction analysis. An alternative mechanism for the formation of dinuclear ruthenium complexes via the insertion of alkenes into the Ru-C(η¹) bond is proposed.

Full text of DOI:10.1021/om100556y

3418 Organometallics 2010, 29, 3418–3430
DOI: 10.1021/om100556y
Pyridyl-Substituted Indenyl Ruthenium Complexes:
Synthesis, Structures, and Reactivities
Dafa Chen,† Xi Zhang,† Shansheng Xu,† Haibin Song,† and Baiquan Wang*,†,‡
†State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University,
Tianjin 300071, People’s Republic of China, and ‡State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032,
People’s Republic of China
Received June 5, 2010
We have investigated the synthesis of a novel pyridyl-substituted indenyl trinuclear ruthenium
complex, {μ2-η5:η1-(C5H4N)(C9H5)}Ru3(CO)9 (1), and its reactivities with pyridine derivatives,
PPh3, and different types of alkenes. Complex 1 was synthesized in 89% yield from Ru3(CO)12
and 3-(2-pyridyl)indene (1:1 mol ratio) in refluxing heptane. The reaction of 1 with a 5-fold excess
of 3-(2-pyridyl)indene gave two complexes, {η1-(C5H4N)(C9H6)}2Ru(CO)2 (2) and {η5-(C5H4N)-
(C9H6)}{η1-(C5H4N)(C9H6)}Ru2(CO)4 (3). Both were also converted back to 1 in the presence of an
equimolar amount of Ru3(CO)12, although the yields were low. Reaction of 1 in refluxing toluene
afforded an unexpected complex, {μ3-η6:η3:η1-(C5H4N)(C9H5)}Ru3(CO)7 (4), via the loss of two CO
groups. Complex 4 represents a completely new type of coordination mode (μ3-η6:η3:η1) of indenyl
ligands in transition metal complexes. The reactions of 1 with 2-(2-pyridyl)indene, 1,2,3,5-tetra-
methyl-4-(2-pyridyl)cyclopentadiene, 1,2-diphenyl-4-(2-pyridyl)cyclopentadiene, and 2-phenylpyr-
idine in refluxing heptane afforded the mono- and/or dinuclear complexes 5-9 via the cleavage of
either a Ru-C(η1) or Ru-C(η5) bond or both. In the case of PPh3, only one of three carbonyls at the
pyridyl-coordinated ruthenium center of 1 was replaced by PPh3 to produce {μ2-η5:η1-(C5H4N)-
(C9H5)}Ru3(CO)8(PPh3) (10). The reactions of 1 with various terminal alkenes (CH2dCHR) gave
only the dinuclear ruthenium complexes {η5-(C5H4N)(C9H5CHCH2R)}Ru2(CO)5 (11-13, 15, and
17) via the insertion of alkenes into the Ru-C(η1) bond of 1 with the exception of 2-vinylpyridine and
CH2dCHOCH2CH3, which reacted with 1 to yield the pyridyl-substituted complex {η5-(C5H4N)-
(C9H5CHCH2(C5H4N))}Ru2(CO)4 (14) and two unexpected complexes, 13 and {η5-(C5H4N)-
(C9H4CHCH2CH2CH(OCH2CH3))}Ru2(CO)5 (18a and 18b), respectively. Complex 15 was also
transformed to {η5-(C5H4N)(C9H5CHCH2CO2CH3)}Ru2(CO)3(η5-CH2dCHCO2CH3) (16) in the
presence of methyl acrylate. The reactions of 1with internal alkenes such as norbornene and cyclohexene
gave complexes 19-22 in very low yields also via the insertion of alkenes into the Ru-C(η1) bond of 1,
with the concomitant formation of a small amount of 4. The molecular structures of 1-5, 8-11, 13-16,
18a, 18b, and 21 were determined by X-ray diffraction analysis. An alternative mechanism for the
formation of dinuclear ruthenium complexes via the insertion of alkenes into the Ru-C(η1) bond is
proposed.
Introduction
reactivities in both stoichiometric and catalytic reactions.1
The cyclopentadienyl or indenyl ligands including periphery
donor substituents have usually been used to synthesize
oligonuclear transition metal complexes possessing distinct
structures and reactivities owing to the favorable intramole-
cular coordination of these donors to Lewis acidic metal
centers.2 In our previous work we studied the reactions of
pyridyl-substituted cyclopentadienes and indenes with Ru3-
(CO)12 and synthesized a series of ruthenium carbonyl
Indenyl metal complexes have received increasing atten-
tion due to their diverse and flexible hapticities and enhanced
*To whom correspondence should be addressed. Fax: þ86-22-
23504781. E-mail: bqwang@nankai.edu.cn.
(1) For recent reviews on the chemistry of indenyl metal complexes,
see: (a) Metallocenes: Synthesis, Reactivity, Applications; Togni, A.;
Halterman, R. L., Eds.; Wiley-VCH: Weinheim, 1998. (b) Bonifaci, C.;
Ceccon, A.; Gambaro, A.; Manoli, F.; Mantovani, L.; Ganis, P.; Santi, S.;
Venzo, A. J. Organomet. Chem. 1998, 557, 97. (c) Calhorda, M. J.; Veiros,
L. F. Coord. Chem. Rev. 1999, 185-186, 37. (d) Cadierno, V.; Diez, J.;
Gamasa, M. P.; Gimeno, J.; Lastra, E. Coord. Chem. Rev. 1999, 193-195,
147. (e) Resconi, L.; Cavallo, L.; Fait, A.; Piemontesi, F. Chem. Rev. 2000,
100, 1253. (f) Stradiotto, M.; Mcglinchey, M. J. Coord. Chem. Rev. 2001,
(2) (a) Jutzi, P.; Siemeling, U. J. Organomet. Chem. 1995, 500, 175.
(b) Jutzi, P.; Redeker, T. Eur. J. Inorg. Chem. 1998, 663. (c) M€uller, C.; Vos,
D.; Jutzi, P. J. Organomet. Chem. 2000, 600, 127. (d) Siemeling, U. Chem.
€
Rev. 2000, 100, 1495. (e) Butenschon, H. Chem. Rev. 2000, 100, 1527. (f)
ꢀ
219-221, 311. (g) Calhorda, M. J.; Felix, V.; Veiros, L. F. Coord. Chem. Rev.
Fischer, P. J.; Krohn, K. M.; Mwenda, E. T.; Young, V. G., Jr. Organome-
tallics 2005, 24, 1776.
2002, 230, 49. (h) Zargarian, D. Coord. Chem. Rev. 2002, 233-234, 157.
r
pubs.acs.org/Organometallics
Published on Web 07/12/2010
2010 American Chemical Society

Article
Organometallics, Vol. 29, No. 15, 2010 3419
Scheme 1
Scheme 2
complexes involving intramolecular C-H activation and
including different bonding modes of indenyl ligands.3 Here-
in we report the synthesis of the pyridyl-substituted indenyl
ruthenium carbonyl complex {μ2-η5:η1-(C5H4N)(C9H5)}-
Ru3(CO)9 (1) and its reactivities with other pyridine deriva-
tives, PPh3, and a series of terminal and internal alkenes.
Results and Discussion
Reaction of 3-(2-pyridyl)indene with Ru3(CO)12. The reac-
tion of 3-(2-pyridyl)indene with Ru3(CO)12 in refluxing
heptane afforded the trinuclear ruthenium complex {μ2-
η5:η1-(C5H4N)(C9H5)}Ru3(CO)9 (1) in 89% yield. The for-
mation of complex 1 involves intramolecular C-H bond
activation and carbonyl substitution by the pyridyl ligand.
Complex 1 could further react with a 5-fold excess of 3-
(2-pyridyl)indene to give the mononuclear complex {η1-(C5-
H4N)(C9H6)}2Ru(CO)2 (2) and the dinuclear complex {η5-
(C5H4N)(C9H6)}{η1-(C5H4N)(C9H6)}Ru2(CO)4 (3) in 41%
and 32% yields, respectively. The formation of 2 involves the
cleavage of both the Ru-C(η1) and Ru-C(η5) bonds of 1,
while for 3 only the Ru-C(η1) bond of 1 is cleaved. Upon
reacting with an equimolar amount of Ru3(CO)12, both
complexes 2 and 3 were converted back to 1 in 45% and
38% yields, respectively (Scheme 1). Note that complexes 2
and 3 should be separated by Al2O3 column chromatography
as quickly as possible since 3 can be easily absorbed by Al2O3
and stuck in the column. Thermal treatment of 1 in reflux-
ing toluene resulted in the unexpected formation of the
complex {μ3-η6:η3:η1-(C5H4N)(C9H5)}Ru3(CO)7 (4) in very
low yield (14%) via the loss of two carbonyl groups and
considerable decomposition of 1 (Scheme 2). Complexes 1-4
were characterized by 1H NMR, IR, elemental analysis, and
single-crystal X-ray diffraction analysis (Figures 1-4), and
Figure 1. ORTEP diagram of 1. Thermal ellipsoids are shown
at the 30% probability level.
Figure 2. ORTEP diagram of 2. Thermal ellipsoids are shown
at the 30% probability level.
analytical data are in good agreement with the proposed
structures. In the trinuclear ruthenium complex 1 (Figure 1),
the pyridyl indenyl ligand behaves as a tridentate cyclome-
talated ligand, which forms a coplanar five-membered ring
(3) (a) Chen, D.; Li, Y.; Wang, B.; Xu, S.; Song, H. Organometallics
2006, 25, 307. (b) Chen, D.; Xu, S.; Song, H.; Wang, B. Eur. J. Inorg. Chem.
2008, 1854.

3420 Organometallics, Vol. 29, No. 15, 2010
Chen et al.
1
˚
˚
length is 2.8244(6) A. The Ru-C(η ) distance is 2.003(5) A,
significantly longer than those in 1 and 2. The pyridyl ring is
no longer coplanar with the η5-indenyl ring plane but with a
dihedral angle of 42.0°. The molecular structure of the trinu-
clear ruthenium complex 4 is very interesting. The pyridyl
indenyl ligand behaves as a tetradentate ligand, and the
indenyl unit itself coordinates with three Ru atoms in an
unprecedented μ3-η6:η3:η1-coordinated mode. The Ru(1)-
Ru(2) and Ru(2)-Ru(3) bond lengths are 2.9038(6) and
1
˚
2.7854(5) A, respectively, while the Ru(3)-C(η ) distance is
˚
2.030(3) A, which are similar to those in 1. The pyridyl ring
plane deviates from the indenyl ring plane by 16.9°. To the
best of our knowledge, this is the first observation of such a
completely new type of ligand-coordination mode in transi-
tion metal complexes. Note that many other indenyl-coordi-
nated modes have been previously reported.1d
Reactions of 1 with Pyridyl Ligands and PPh3. The reac-
tivity of 2-(2-pyridyl)indene with complex 1 is very similar to
that of its 3-positional isomer, 3-(2-pyridyl)indene. Two
ruthenium products, 5 and 6, were obtained in 41% and
29% yields, respectively. The formation of 5 and 6 is highly
likely to involve the same mechanisms as that of their analo-
gues 2 and 3 (Scheme 3). In comparison with pyridyl indenes,
1,2,3,5-tetramethyl-4-(2-pyridyl)cyclopentadiene reacted with
complex 1 to afford only the dinuclear ruthenium complex
[η5-(2-pyridyl)tetramethylcyclopentadienyl][η1-1-(2-pyridyl)-
indenyl]Ru2(CO)4 (7), an analogue of both complexes 3 and
6 (Scheme 4). We did not observe the formation of the
mononuclear analogue of both complexes 2 and 5, which is
due to the impossible C-H bond activation of the per-
substituted cyclopentadiene. The reaction of 1,2-diphenyl-
4-(2-pyridyl)cyclopentadiene with 1 was completely different
from those of other pyridyl-cyclopentadienyl derivatives
including indenes, and only the common cyclopentadienyl
dicarbonyl ruthenium dimer 8 was formed. In complex 8, the
pyridyl group behaves as an aryl substituent rather than a
ligand coordinating to a ruthenium atom. 2-Phenylpyridine
reacted with 1 to give only the bis(η1-2-pyridylphenyl)rut-
henium complex 9 via C-H bond activation at the phenyl
ring (Scheme 4). These results indicate that the C-H bond
activation by ruthenium complexes can readily take place at
an sp2 hybridized carbon atom. The reaction of 1 with PPh3
in refluxing toluene gave only the PPh3-substituted analogue 10.
In this reaction we did not observe the formation of com-
plex 4 and/or its PPh3-substituted analogue even in refluxing
toluene for 30 h, indicating that PPh3 might stabilize com-
plexes 1 and 10 and halt their transformation to the products
(e.g., 4) with the new type of μ3-η6:η3:η1-coordinated mode
by rejecting two carbonyl groups. Complexes 5-10 were
characterized by 1H NMR, IR, and elemental analysis. The
31P NMR spectrum of 10 showed a singlet at -26.85 ppm, a
characteristic resonance signal for PPh3 coordinating to a
ruthenium atom.5 The molecular structures of 5 and 8-10
were also determined by single-crystal X-ray diffraction an-
alysis (Figures 5-8). The structures of 5 and 9 are similar to
that of 2, containing two cyclometalated pyridyl indenyl or
phenyl pyridyl ligands and two cis carbonyl groups. The
Ru-C(η1) distances are 2.057(2), 2.093(2) and 2.064(4),
Figure 3. ORTEP diagram of 3. Thermal ellipsoids are shown
at the 30% probability level.
Figure 4. ORTEP diagram of 4. Thermal ellipsoids are shown
at the 30% probability level.
with Ru(3) and also coordinates with Ru(1) in η5 mode. Both
Ru(2) and Ru(3) atoms adopt a pseudooctahedral coordi-
nated mode. The Ru(1)-Ru(2) and Ru(2)-Ru(3) bond
˚
lengths are 2.8251(5) and 2.9393(5) A, respectively. The
1
˚
Ru(3)-C(η ) distance is 2.078(3) A, much shorter than those
of Ru(1)-C(η ) (2.239-2.332 A). The mononuclear ruthe-
5
˚
nium complex 2 (Figure 2) contains two cyclometalated
pyridyl indenyl ligands that are perpendicular to each other
and two cis carbonyl groups. Its pseudooctahedral-coordi-
nated mode is very similar to that found in the complex
Ru(CO)2(BQ)2 (BQ = benzo[h]quinoline).4 The Ru-C(η1)
˚
distances are 2.032(3) and 2.080(3) A, respectively. In the
dinuclear ruthenium complex 3 (Figure 3), both pyridyl
indenyl ligands behave as a bidentate ligand, but the co-
ordinated modes of their five-membered ring are quite
different. The one with η5 mode forms a bimetalated cycle
including both ruthenium atoms, while the other, with η1
mode, forms a five-membered cyclometalated ring with Ru(2),
as found in complexes 1 and 2. The Ru(1)-Ru(2) bond
˚
2.105(4) A, respectively, slightly longer than those in 2.
Complex 8 is a 1,2-diphenyl-4-(2-pyridyl)cyclopentadienyl
dicarbonyl ruthenium dimer with a Ru-Ru bond length of
(4) Li, E. Y.; Cheng, Y.-M.; Hsu, C.-C.; Chou, P.-T.; Lee, G.-H.; Lin,
I.-H.; Chi, Y.; Liu, C.-S. Inorg. Chem. 2006, 45, 8041.
(5) Phillips, G.; Hermans, S.; Adams, J. R.; Johnson, B. F. G. Inorg.
Chim. Acta 2003, 352, 110.

Article
Organometallics, Vol. 29, No. 15, 2010 3421
Scheme 3
Scheme 4
Figure 5. ORTEP diagram of 5. Thermal ellipsoids are shown
at the 30% probability level.
˚
2.7478(6) A. It adopts a cis configuration with the two
Figure 6. ORTEP diagram of 8. Thermal ellipsoids are shown
at the 30% probability level.
substituted cyclopentadienyl groups on the same side. The
structure of 10 (Figure 8) shows that one of the three
carbonyl groups at Ru(3) is replaced by PPh3, indicating
that the carbonyl groups at the pyridyl-coordinated ruthe-
nium center are more reactive toward ligand substitution
than those at other ruthenium centers.
Reactions of 1 with Alkenes. In the previous section we
have shown that various types of pyridyl ligands are capable
of breaking both the Ru-C(η1) and Ru-C(η5) bonds of
complex 1 to form novel ruthenium complexes. In this
section we have investigated the reactivity of 1 with a series
of terminal and internal alkenes.
15, and 17) via the insertion of alkenes into the Ru-C(η1)
bond of complex 1 with the exception of 2-vinylpyridine and
CH2dCHOCH2CH3 (entries 1-7 in Table 1). In the case of
2-vinylpyridine, the pyridyl-substituted complex {η5-(C5H4N)-
(C9H5CHCH2(C5H4N))}Ru2(CO)4 (14) (entry 4 in Table 1)
was obtained in 58% yield via intramolecular CO substitu-
tion by the pyridyl unit of 2-vinylpyridine. The reaction of 1
with CH2dCHOCH2CH3 was completely different from
those of 1 with other terminal alkenes; two anomalous in-
sertion products, 13 and 18 (entry 7 in Table 1), were un-
expectedly formed, both as a mixture of two isomers. It is
obvious that the formation of 13 involves the cleavage of
the C-O bond at the ethylene side of CH2dCHOCH2CH3
The reactions of 1 with various terminal alkenes (CH2d
CHR) in refluxing toluene gave only the dinuclear ruthenium
complexes {η5-(C5H4N)(C9H5CHCH2R)}Ru2(CO)5 (11-13,

3422 Organometallics, Vol. 29, No. 15, 2010
Chen et al.
transformed to the complex {η5-(C5H4N)(C9H5CHCH2-
CO2CH3)}Ru2(CO)3(η3-CH2dCHCO2CH3) (16) (entry 5
in Table 1), in which two carbonyl groups were replaced by
a methyl acrylate molecule.
The reactions of 1 with internal alkenes such as norbor-
nene and cyclohexene gave complexes 19-22 (entries 8-11
in Table 1) in low yields also via the insertion of alkenes into
the Ru-C(η1) bond, together with the concomitant forma-
tion of a small amount of 4. This indicates that the reactivity
of 1 with internal alkenes is much lower than with terminal
alkenes presumably due to the steric effect of internal
alkenes. This hypothesis is further supported by the reac-
tion of 1 with a very bulky four-substituted alkene, 2,3,4,5-
tetramethylcyclopent-2-enone, which afforded only 4 in
14% yield (entry 12 in Table 1). When 1 reacted with a con-
jugated alkene, 6,60-dimethylbenzofulvene, the complex {η5-
(C5H4N)(C9H5-C12H12)}Ru2(CO)5 (21) was obtained (entry
10 in Table 1). The reaction of 1 with (E)-2-hexene gave
{η5-(C5H4N)(C9H5-C6H12)}Ru2(CO)5 (22) (entry 11 in
Table 1), which is similar to complex 12, forming via the
reaction of 1 with 1-hexene. Therefore, the formation of 22
may involve the initial ruthenium-catalyzed isomerization of
2-hexene to 1-hexene and subsequent insertion of 1-hexene
into the Ru-C(η1) bond of complex 1. This type of isomer-
ization of a double bond is very common and has been
previously reported.8-11
Figure 7. ORTEP diagram of 9. Thermal ellipsoids are shown
at the 30% probability level.
1
All new complexes were characterized by H NMR, IR,
and elemental analysis. The molecular structures of 11,
13-16, 18a, 18b, and 21 were further determined by single-
1
crystal X-ray diffraction analysis (Figures 9-16). The H
NMR spectra of the alkene-insertion products from terminal
alkenes show characteristic resonance signals in the range
2.59-3.41 ppm (e.g., triplets for 11 (3.02 ppm), 12 (2.72
ppm), 16 (3.41 ppm), and 22 (2.73 ppm); double doublet for
14 (4.02 ppm); quartets for 13 (2.79 and 2.59 ppm)) for Ru-
CH protons, indicating a 1,1-insertion mode. In the 1H
NMR spectrum of 17, the signal of the Ru-CH proton is
overlapped with that of the adjacent proton, but the doublet
at 1.49 ppm for the methyl protons clearly indicates the
presence of the CH3CH(CO2Me)CH unit, which strongly
supports the 1,1-insertion mode too. The alkene-insertion
reaction generates a new chiral carbon atom σ-bonded to the
Ru atom in all complexes except for 20, enabling them to
exist as a mixture of two isomers theoretically if there are no
additional chiral centers in their molecules. However, only
complex 13 was found to exist as a mixture of two isomers in
the ratio of ∼8:1, determined by comparing the characteristic
1H resonance signals of the Cp-ring, Ru-CH, and CH3
protons of two isomers. It should be noted that complex
13, forming from the reaction of 1 with CH2dCHOCH2CH3,
also exists as a mixture of two isomers in the ratio ∼3:2.
Unfortunately the two isomers of 13 could not be separated
either by preparative TLC due to their almost equal Rf values
or by recrystallization. A single crystal of the major isomer of
13 was accidently picked up for X-ray diffraction analysis.
There exists only one isomer for other complexes probably
due to the steric effect of the substituents at the chiral carbon.
The molecular structures of 11, 13-16, 18a, 18b, and 21 have
similar frameworks, containing two ruthenium atoms with
Figure 8. ORTEP diagram of 10. Thermal ellipsoids are shown
at the 60% probability level.
because 13 is also the product from the reaction of 1 with
ethylene gas. Complex 18 includes a newly formed six-
membered ring fused to the five-membered ring of the
indenyl ligand and an additional chiral carbon center adja-
cent to the five-membered ring. Therefore, it is a mixture of
two diastereomers, 18a and 18b, which were readily sepa-
rated by flash column chromatography. In comparison with
the expected insertion product {η5-(C5H4N)(C9H5CHCH2-
OCH2CH3)}Ru2(CO)5, which was not formed in the reaction
of 1 with CH2dCHOCH2CH3, two more carbon atoms were
increased in the molecule of 18. This indicates that the
formation of 18 might involve the same intermediates in
the formation of 13 and ruthenium-mediated C-C coupling.
However, the detailed mechanisms for the formation of both
13 and 18 still remain unclear. It was found that complex 15
in the presence of an excess of methyl acrylate could be
˚
Ru-Ru bond lengths of 2.7879-2.8162 A, an intramolecu-
lar coordinated pyridyl, and a cyclometalated unit with the
bulky substituents at the chiral carbon deviating away from
the pyridyl unit to reduce intramolecular interaction between
them. The dihedral angles between the pyridyl ring and the

Article
Organometallics, Vol. 29, No. 15, 2010 3423
Table 1. Reactions of 1 with Alkenes
indenyl ring planes are 32.1-40.0°. The molecular structure
of 14 (Figure 11) shows that one of the three carbonyl groups
at the Ru(2) atom is replaced by the pyridyl group from vinyl
pyridine, strongly supporting that carbonyl groups at the
pyridyl-coordinated ruthenium center are more reactive
toward ligand substitution than at the other ruthenium
center (see also for complex 10). The molecular structure of
complex 16 (Figure 13) contains a methyl acrylate ligand
coordinating to two ruthenium atoms in η3-coordinated
˚
mode. Although the C(22)-C(23) bond length (1.396(5) A)

3424 Organometallics, Vol. 29, No. 15, 2010
Chen et al.
Figure 9. ORTEP diagram of 11. Thermal ellipsoids are shown
at the 30% probability level.
Figure 12. ORTEP diagram of one isomer of 15. Thermal
ellipsoids are shown at the 50% probability level.
Figure 10. ORTEP diagram of 13. Thermal ellipsoids are
shown at the 15% probability level.
Figure 13. ORTEP diagram of 16. Thermal ellipsoids are
shown at the 30% probability level.
Figure 14. ORTEP diagram of 18a. Thermal ellipsoids are
shown at the 30% probability level.
Figure 11. ORTEP diagram of 14. Thermal ellipsoids are
shown at the 30% probability level.
noncoordinated ester carbonyl in 16) due to the coordination
of O(6) to Ru(2). The coordination of the oxygen atom of
methyl acrylate instead of a carbonyl decreases the intramole-
in the methyl acrylate ligand is comparable to those in other
η2-coordinated alkenes,6,7 the C(24)-O(6) bond is signifi-
3
˚
˚
cantly elongated (1.226(4) vs 1.180(5) A for C(20)-O(4), a
cular interaction and makes the Ru-C(sp ) bond (2.086(4) A)

Article
Organometallics, Vol. 29, No. 15, 2010 3425
structure of 21 (Figure 16) suggests that its formation
involves a 1,4-hydrogen shift to form an isopropyl group
and an endocyclic double bond instead of a 1,2-hydrogen
shift generally found for nonconjugated alkenes. To reduce
steric interaction near the chiral carbon center, the phenyl
ring in 6,60-dimethylbenzofulvene is also deviated away from
the pyridyl unit. However, the intramolecular interaction in
3
˚
21 is still large and makes the Ru-C(sp ) bond (2.238(4) A)
much longer than those of others.
No reaction was observed between 2 or 3 and styrene,
indicating that the indenyl ligand with both η5- and η1-coordi-
nated modes is essential for alkene-insertion reactions. The
reaction of 3-(2-pyridyl)indene with styrene in the presence of a
catalytic amount of Ru3(CO)12 did not form the C-H/alkene
coupling product, and only a small amount of 2 was obtained
together with the recovery of the starting materials. This result
indicates that 3-(2-pyridyl)indene is not suitable for Ru3(CO)12-
catalyzed C-H/alkene coupling reactions since it quickly reacts
with Ru3(CO)12 to form 1 with the elimination of two H atoms,
which is further transformed to complexes 2 and 3 in the
presence of an excess amount of 3-(2-pyridyl)indene.
Figure 15. ORTEP diagram of 18b. Thermal ellipsoids are
shown at the 30% probability level.
An Alternative Mechanism for Alkene Insertion Reactions.
Functional group-directed Ru-catalyzed aromatic C-H/al-
kene coupling reactions generally lead to the hydroarylation
of olefins, most likely via a hydrometalation mechanism
involving (i) the initial activation of aromatic C-H bonds
by ruthenium complexes, (ii) the subsequent insertion of
olefins into the formed Ru-H bond, and (iii) the final
reductive elimination to liberate the coupling products as well
as the ruthenium catalyts.12-14 However, in some cases the
arylation of olefins occurs to give the dehydrogenative cou-
pling products,12,15,16 which were believed to be formed via
β-H elimination from carbometalated intermediates resulting
from the insertion of alkenes into the Ru-C bond. On the
basis of the previously reported mechanism on ruthenium-
catalyzed C-H/alkene coupling reactions, we propose an
alternative mechanism (Scheme 517) to account for the inser-
tion reactions of alkenes into the Ru-C(η1) bond of complex 1.
We have known that in complex 1 the carbonyl groups at the
pyridyl-coordinated ruthenium atom are more reactive to-
ward ligand substitution, so initial CO substitution by alkenes
at this ruthenium center should easily take place to form the
olefin-coordinated ruthenium intermediate, which could be
transformed to the carbometalation intermediates 23 via the
intramolecular insertion of the alkenes into the Ru-C(η1)
bond. Note that this insertion process should be highly
regioselective with the R groups far away from the indenyl
ligand since there are only 1,1-insertion products formed
with all terminal alkenes. The intermediate 23 undergoes
β-H elimination to form the alkene-coordinated ruthenium
hydride complex 24. Finally, the insertion of olefins into the
Ru-H bond gives the 1,1-insertion products.
Figure 16. ORTEP diagram of 21. Thermal ellipsoids are
shown at the 30% probability level.
˚
much shorter than those of others (2.142-2.197 A for 11,
13-15, 18a, and 18b). The molecular structures of the two
diastereomers 18a and 18b (Figures 14 and 15) are very
similar, and the only difference is that two hydrogens
attached to the two chiral carbon centers are cis with respect
to the indenyl plane in 18a but trans in 18b. The molecular
(6) Hauptman, E.; Sabo-Etienne, S.; White, P. S.; Brookhart, M.;
Garner, J. M.; Fagan, P. J.; Calabrese, J. C. J. Am. Chem. Soc. 1994, 116,
8038.
(7) (a) Foley, N. A.; Lail, M.; Lee, J. P.; Gunnoe, T. B.; Cundari,
T. R.; Petersen, J. L. J. Am. Chem. Soc. 2007, 129, 6765. (b) McWilliams,
K. M.; Ellern, A.; Angelici, R. J. Organometallics 2007, 26, 1665.
(8) Jun, C.-H.; Hwang, D.-C.; Na, S.-J. Chem. Commun. 1998, 1405.
(9) Chatani, N.; Asaumi, T.; Yorimitsu, S.; Ikeda, T.; Kakiuchi, F.;
Murai, S. J. Am. Chem. Soc. 2001, 123, 10935.
(12) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. Rev. 2002, 102, 1731.
(13) Kakiuchi, F.; Murai, S. Acc. Chem. Res. 2002, 35, 826, and
references therein..
(14) Guari, Y.; Castellanos, A.; Sabo-Etienne, S.; Chaudret, B.
J. Mol. Catal. A 2004, 212, 77.
(15) Kakiuchi, F.; Sato, T.; Yamauchi, M.; Chatani, N.; Murai, S.
Chem. Lett. 1999, 19.
(10) (a) Reger, D. L.; Garza, D. G.; Baxter, J. C. Organometallics
ꢀ
1990, 9, 873. (b) Royo, E.; Acebron, S.; Mosquera, M. E. G.; Royo, P.
(16) (a) Ritleng, V.; Sutter, J. P.; Pfeffer, M.; Sirlin, C. Chem.
Commun. 2000, 129. (b) Ritleng, V.; Pfeffer, M.; Sirlin, C. Organometallic
2003, 22, 347.
(17) Since we do not know how the third ruthenium atom is lost in the
formation of insertion products, only the partial molecular skeletons are
shown in Scheme 5 for clarity and easier understanding.
Organometallics 2007, 26, 3831.
(11) For recent papers on the chemistry of double-bond migration,
ꢀ
see: (a) Krompiec, S.; Kuznik, N.; Krompiec, M.; Penczek, R.; Mrzigod,
ꢀ
J.; Torz, A. J. Mol. Catal. A 2006, 253, 132. (b) Kuꢀznik, N.; Krompiec, S.
Coord. Chem. Rev. 2007, 251, 222.

3426 Organometallics, Vol. 29, No. 15, 2010
Chen et al.
Scheme 5
This mechanism can well account for the formation of
insertion products for open-chain alkenes, but it is difficult
to explain the insertion of cyclic alkenes. In general, alkene
insertion into an M-C bond proceeds via a syn process, and
the β-H elimination of transition metal alkyl complexes
needs the syn coplanar (or nearly coplanar) arrangement of
the M-CR-Cβ-H atoms.18 For cyclic alkenes such as
norbornene, syn insertion will not generate the product
possessing a syn hydrogen for β-H elimination. It is known
that in some cases R-H elimination may compete with β-H
elimination. However, the insertion reaction with methyl
methacrylate (MMA) also produced only the 1,1-insertion
product in good yield, which rules out the possibility of R-H
elimination because the corresponding intermediate 23 with
MMA insertion does not have any R-H for elimination.
Furthermore, for cyclic alkenes it is still possible for anti
β-H elimination to occur at high temperature (110 °C) even
though the rate might be very low. This may explain low
yields (7-18%) for insertion products and the formation of a
small amount of 4 for all cyclic alkenes. In fact there were
some reports on the anti β-H elimination.19
Although the alternative mechanism appears successful in
explaining the formation of the 1,1-insertion products from
different types of olefins and is also in good agreement with
the previously reported mechanisms on aromatic C-H/
alkene coupling reactions, we cannot completely rule out
other potential possibilities since currently we do not know
how the third ruthenium atom in complex 1 is ejected and it is
still uncertain whether more ruthenium atoms in complex 1
participate in this novel chemical transformation.
with pyridine derivatives, PPh3, and different types of alkenes.
It was found that complex 1 could be readily converted to two
ruthenium complexes, 2 and 3, in the presence of an excess
amount of 3-(2-pyridyl)indene, and both could be also con-
verted back to 1. Thermal treatment of 1 in refluxing toluene
generated an unexpected ruthenium complex, {μ3-η6:η3:η1-
(C5H4N)(C9H5)}Ru3(CO)7 (4), by ejecting two carbonyl
groups. To the best of our knowledge, complex 4 represents
a completely new type of coordination mode (μ3-η6:η3:η1) of
indenyl ligands in transition metal complexes. In complex 1,
carbonyl groups at the pyridyl-coordinated ruthenium center
are more reactive toward ligand substitution (e.g., PPh3) than
those at other ruthenium centers. Complex 1 reacted with
different types of alkenes to produce the dinuclear complexes
including a newly formed C-C bond via the insertion of the
alkenes into the Ru-C(η1) bond of 1. It should be noted
that the reaction of 1 with the alkene CH2dCHOCH2CH3
generated two unexpected complexes, {η5-(C5H4N)(C9H5-
CHCH3)}Ru2(CO)5 (13) and {η5-(C5H4N)(C9H4CHCH2-
OCH2CH(OCH2CH3))} Ru2(CO)5 (18a and 18b), respec-
tively. Methyl acrylate was found to coordinate to the two
ruthenium atoms of complex 16 in η3-coordinated mode. The
reaction of 1 with a conjugated alkene, 6,60-dimethylbenzo-
fulvene, afforded the complex {η5-(C5H4N)(C9H5-C12H12)}-
Ru2(CO)5 (21) via 1,4-hydrogen shift instead of the 1,2-
hydrogen shift generally found for nonconjugated alkenes.
The reaction of 1 with (E)-2-hexene may involve initial
ruthenium-catalyzed olefin isomerization and subsequent
olefin insertion. An alternative mechanism for the formation
of dinuclear ruthenium complexes via the insertion of alkenes
into the Ru-C(η1) bond of 1 is proposed. This work high-
lights the diversified reactivities of pyridyl-substituted indenyl
ruthenium complexes and provides mechanistic insights into
Ru-mediated olefin-involved organic reactions.
Conclusions
In summary, we have synthesized a novel pyridyl-substi-
tuted indenyl trinuclear ruthenium complex, {μ2-η5:η1-
(C5H4N)(C9H5)}Ru3(CO)9 (1), andinvestigateditsreactivities
Experimental Section
General Considerations. Schlenk and vacuum line techniques
were employed for all manipulations of air- and moisture-
sensitive compounds. All solvents were distilled from appro-
priate drying agents under argon before use. 1H NMR spectra
were recorded on Bruker AV300 or Varian AS-400 instruments,
while IR spectra were recorded in CH2Cl2 solution on a Nicolet
380 FT-IR spectrometer. ESI mass spectra were recorded on a
(18) Kuznetsov, V. F.; Abdur-Rashid, K.; Lough, A. J.; Gusev, D. G.
J. Am. Chem. Soc. 2006, 128, 14388.
(19) (a) Friestad, G. K.; Branchaud, B. P. Tetrahedron Lett. 1995, 36,
7047, and references therein.. (b) Takacs, J. M.; Lawson, E. C.; Clement, F.
J. Am. Chem. Soc. 1997, 119, 5956. (c) Lautens, M.; Fang, Y.-Q. Org. Lett.
2003, 5, 3679, and references therein.. (d) Tanaka, D.; Romeril, S. P.; Myers,
A. G. J. Am. Chem. Soc. 2005, 127, 10323. (e) Review: Ikeda, M.; El Bialy,
S. A. A.; Yakura, T. Heterocycles 1999, 51, 1957.

Article
Organometallics, Vol. 29, No. 15, 2010 3427
Thermo Finnigan LCQ Advantage mass spectrometer. Elemen-
tal analyses were performed on a Perkin-Elmer 240C analyzer.
3-(2-Pyridyl)indene, 2-(2-pyridyl)indene, 1,2,3,5-tetramethyl-
4-(2-pyridyl)cyclopentadiene, and 3,4-diphenylcyclopentenone
were synthesized according to literature procedures.20-23
Synthesis of 1,2-Diphenyl-4-(2-pyridyl)cyclopentadiene. A so-
lution of 8.9 g (56.4 mmol) of 2-bromopyridine in 50 mL of Et2O
was added to a solution of 30 mL of n-BuLi (1.88 mol/L, 56.4
mmol) in hexane at -60 °C. After stirring for 0.5 h at this
temperature, a solution of 13.2 g (56.4 mmol) of 3,4-diphenyl-
cyclopentenone in 80 mL of THF was added dropwise. After
stirring at -60 to -40 °C for 3 h, the mixture was warmed slowly
to room temperature and stirred overnight. To the mixture was
added slowly 50 mL of a saturated NH4Cl aqueous solution;
then it was separated, and the organic phase was dried over
Na2SO4. After filtration the solvents were removed under
reduced pressure. The residue was recrystallized with CH2Cl2/
hexanetogive5.8g(35%) of4as yellow crystals. Mp: 130-131 °C.
Anal. Calcd for C22H17N: C, 89.46; H, 5.80; N, 4.74. Found: C,
89.15; H, 5.70, N, 4.71. 1H NMR (300 MHz, CDCl3): δ 8.59 (d,
J = 3.7 Hz, 1H, Py-H), 7.67 (t, J = 6.8, 6.9 Hz, 1H, Py-H), 7.58
(d, J = 7.8 Hz, 1H, Py-H), 7.46-7.06 (m, 12H) (Py-H, Ph-H, and
C5 ring H), 4.11 (s, 2H, C5 ring H). 13C NMR (CDCl3): δ 154.1,
149.5, 145.3, 141.9, 141.7, 137.0, 136.6, 136.3, 135.7, 128.5, 128.4,
128.3, 127.9, 127.3, 126.8, 121.3, 119.5, 44.8. MS (ESI): m/z 296
(Mþ þ H).
J = 23.6 Hz, 1H, Cp-H). IR (νCO, cm-1): 1996(s), 1960 (s),
1917(s), 1898(s).
Reaction of 2 with Ru3(CO)12. A solution of 0.060 g (0.11
mmol) of 2 and 0.12 g (0.19 mmol) of Ru3(CO)12 in 20 mL of
heptane was refluxed for 40 h. The solvent was removed under
reduced pressure, and the residue was placed in an Al2O3
column. Elution with CH2Cl2/petroleum ether gave 0.080 g
(45%) of 1.
Reaction of 3 with Ru3(CO)12. A solution of 0.050 g (0.071
mmol) of 3 and 0.061 g (0.095 mmol) of Ru3(CO)12 in 20 mL of
heptane was refluxed for 30 h. The solvent was removed under
reduced pressure, and the residue was placed in an Al2O3
column. Elution with CH2Cl2/petroleum ether gave 0.040 g
(38%) of 1.
Thermal Reaction of 1. A solution of 0.20 g (0.27 mmol) of 1 in
20 mL of toluene was refluxed for 25 h. The solvent was removed
under reduced pressure, and the residue was placed in an Al2O3
column. Elution with CH2Cl2/petroleum ether gave 0.025 g
(14%) of 4 as orange crystals. Mp: 125-126 °C. Anal. Calcd
for C21H9NO7Ru3: C, 36.53; H, 1.31; N, 2.03. Found: C, 36.40;
H, 1.48; N, 2.18. 1H NMR (CDCl3): δ 8.36 (d, J = 5.6 Hz, 1H,
Py-H), 7.58 (t, J = 7.7 Hz, 1H, Py-H), 7.06 (d, J = 7.7 Hz, 1H,
Py-H), 6.85 (t, J = 5.6 Hz, 1H, Py-H), 6.15 (m, 2H, Ar-H), 4.89
(s, 1H, Cp-H), 4.57 (t, J = 6.1 Hz, 2H, Ar-H). IR (νCO, cm-1):
2062(s), 1986(s), 1964(m), 1953(m), 1921(s), 1900(m).
Reaction of 1 with 2-(2-Pyridyl)indene. Using a procedure
similar to that described above, reaction of 0.20 g (0.27 mmol) of
1 with 0.26 g (1.3 mmol) of 2-(2-pyridyl)indene in 30 mL of
heptane gave 0.20 g (41%) of 5 and 0.080 g (29%) of 6 as yellow
and orange crystals, respectively.
Synthesis of 1. A solution of 0.091 g (0.47 mmol) of 3-(2-
pyridyl)indene and 0.30 g (0.47 mmol) of Ru3(CO)12 in 30 mL of
heptane was refluxed for 3 h. The solvent was removed under
reduced pressure, and the residue was placed in an Al2O3
column. Elution with CH2Cl2/petroleum ether developed a
yellow band, which gave 0.31 g (89%) of 1 as orange crystals.
Mp: 145 °C (dec). Anal. Calcd for C23H9NO9Ru3: C, 37.00; H,
1.22; N, 1.88. Found: C, 37.24; H, 1.29; N, 2.14. 1H NMR
(CDCl3): δ 8.60 (d, J = 5.9 Hz, 1H, Py-H), [7.93 (m, 2H), 7.79 (t,
1H, J = 7.7 Hz, 1H), 7.59 (d, J = 7.7 Hz, 1H), 7.33-7.23 (m,
2H), 7.08 (t, 1H, J = 5.9 Hz, 1H)] (Py-H and Ar-H), 5.64 (s, 1H,
Cp-H). IR (νCO, cm-1): 2086(s), 2050(s), 1995(s), 1981(s),
1966(s), 1915(s).
Reaction of 1 with 3-(2-Pyridyl)indene. A solution of 0.20 g
(0.27 mmol) of 1 and 0.26 g (1.3 mmol) of 3-(2-pyridyl)indene in
30 mL of heptane was refluxed for 12 h. The solvent was
removed under reduced pressure, and the residue was placed
in an Al2O3 column. Elution with CH2Cl2/petroleum ether
developed a yellow band and an orange band, which gave 0.18 g
(41%) of 2 and 0.090 g (32%) of 3 as yellow and orange crystals,
respectively.
Complex 2: mp 190-191 °C. Anal. Calcd for C30H20N2O2Ru:
C, 66.53; H, 3.72; N, 5.17. Found: C, 66.42; H, 3.50; N, 5.20. 1H
NMR (CDCl3): δ 8.99 (d, J = 5.0 Hz, 1H, Py-H), 8.01 (d, J =
8.1 Hz, 1H, Py-H), [7.95 (t, J = 8.1 Hz, 1H), 7.83 (d, J = 8.1 Hz,
1H), 7.67-7.56 (m, 4H), 7.38-7.19 (m, 5H), 7.14 (t, J = 7.6 Hz,
1H), 6.97 (t, J = 7.6 Hz, 1H), 6.65 (t, J = 6.0 Hz, 1H)] (Py-H and
Ar-H), 4.27 (d, J = 23.6 Hz, 1H, Cp-H), 4.13 (d, J = 23.6 Hz,
1H, Cp-H), 3.31 (d, J = 24.2 Hz, 1H, Cp-H), 3.02 (d, J = 24.2
Hz, 1H,Cp-H). IR (νCO, cm-1): 2004(s), 1946(s).
Complex 5: mp 160-161 °C. Anal. Calcd for C30H20N2O2Ru:
C, 66.53; H, 3.72; N, 5.17. Found: C, 66.42; H, 3.50; N, 5.20. 1H
NMR (300 MHz, CDCl3): δ 8.91 (d, J = 5.4 Hz, 1H, Py-H), 8.17
(d, J = 7.5 Hz, 1H, Py-H), 7.81 (m, 1H, Py-H), 7.60 (d, J = 7.0
Hz, 1H, Py-H), 7.48-7.40 (m, 3H, Py-H), 7.35 (dd, J = 7.4, 1.0
Hz, 1H, Py-H), 7.30 (m, 1H, Ar-H), 7.19-7.08 (m, 3H, Ar-H),
6.95 (m, 1H, Ar-H), 6.78 (t, J = 7.4 Hz, 1H, Ar-H), 6.65 (d, J =
7.5 Hz, 1H, Ar-H), 6.53 (m, 1H, Ar-H), 3.69 (s, 2H, Cp-H), 3.49
(d, J = 13.0 Hz, 2H, Cp-H). IR (νCO, cm-1): 2009(s), 1947(s).
Complex 6: mp 190-191 °C. Anal. Calcd for C32H20-
N2O4Ru2: C, 55.01; H, 2.89; N, 4.01. Found: C, 54.99; H,
1
2.70; N, 4.11. H NMR (400 M Hz, CDCl3): δ 8.90 (d, J =
4.7 Hz, 1H, Py-H), 8.04 (d, J = 7.7 Hz, 1H, Py-H), 7.83 (t, J =
7.3. 8.0 Hz, 1H, Py-H), 7.59 (t, J = 7.4, 7.8 Hz, 1H, Py-H),
7.50-7.20 (m, 8H, Py-H and Ar-H), 7.18 (t, J = 7.1, 7.3 Hz, 1H,
Ar-H), 7.06 (t, J = 7.1, 7.9 Hz, 1H, Ar-H), 6.97 (t, J = 7.1, 7.9
Hz, 1H, Ar-H), 6.69 (t, J = 6.2, 6.3 Hz, 1H, Ar-H), 5.45 (s, 1H,
Cp-H), 5.04 (s, 1H, Cp-H), 3.64 (d, J = 5.5 Hz, 2H, Cp-H). IR
(νCO, cm-1): 2015(s), 1959(s), 1917(s), 1898(s).
Reaction of 1 with 1,2,3,5-Tetramethyl-4-(2-pyridyl)cyclo-
pentadiene. Using a procedure similar to that described above,
reaction of 0.25 g (0.33 mmol) of 1 with 0.34 g (1.7 mmol) of
1,2,3,5-tetramethyl-4-(2-pyridyl)cyclopentadiene in 30 mL of
heptane gave 0.12 g (52%) of 7 as yellow crystals. Mp: 175 °C
(dec). Anal. Calcd for C32H26N2O4Ru2: C, 54.54; H, 3.72; N,
1
3.98. Found: C, 54.34; H, 3.80; N, 3.93. H NMR (300 MHz,
Complex 3: mp 170-171 °C. Anal. Calcd for C32H20
N2O4Ru2: C, 55.01; H, 2.89; N, 4.01. Found: C, 54.98; H,
2.60; N, 4.14. H NMR (CDCl3): δ 8.93 (d, J = 5.5 Hz, 1H,
Py-H), [7.92 (m, 2H), 7.72-6.96 (m, 10H), 6.89 (t, J = 7.1 Hz,
1H), 6.81 (d, J = 5.5 Hz, 1H), 6.71 (t, J = 7.1 Hz, 1H)] (Py-H
and Ar-H), 6.08 (d, J = 3.0 Hz, 1H, Cp-H), 5.70 (d, J = 3.0 Hz,
1H, Cp-H), 4.15 (d, J = 23.6 Hz, 1H, Cp-H), 3.75 (d,
-
CDCl3): δ 8.96 (d, J = 5.1 Hz, 1H, Py-H), 7.98 (d, J = 8.2 Hz,
1H, Py-H), 7.85 (m, 1H, Py-H), 7.62 (m, 2H, Py-H), 7.45-7.39
(m, 2H, Py-H), 7.34 (d, J = 7.7 Hz, 1H, Py-H), 7.27-7.20 (m,
2H, Ar-H), 7.00 (t, J = 7.2, 7.4 Hz, 1H, Ar-H), 6.58 (t, J = 6.1,
6.7 Hz, 1H, Ar-H), 4.18 (d, J = 23.5 Hz, 1H, Cp-H), 3.81 (d, J =
23.5 Hz, 1H, Cp-H), 2.11 (s, 3H, Me), 2.04 (s, 3H, Me), 1.86 (s,
3H, Me), 1.54 (s, 3H, Me). IR (νCO, cm-1): 1986(s), 1942(s),
1922(s), 1886(s).
1
€
(20) Dreier, T.; Frohlich, R.; Erker, G. J. Organomet. Chem. 2001,
621, 197.
Reaction of 1 with 1,2-Diphenyl-4-(2-pyridyl)cyclopentadiene.
Using a procedure similar to that described above, reaction of
0.20 g (0.26 mmol) of 1 with 0.40 g (1.4 mmol) of 1,2-diphenyl-
4-(2-pyridyl)cyclopentadiene in 30 mL of heptane gave 0.25 g
(71% based on Ru) of 8 as red crystals. Mp: 256-257 °C.
Anal. Calcd for C48H32N2O4Ru2: C, 63.85; H, 3.57; N, 3.10.
(21) Schottek, J.; Kratzer, R. US 6458982, 2002.
(22) Siemeling, U.; Vorfeld, U.; Neumann, B.; Stammler, H.-G.
Chem. Ber. 1995, 128, 481.
(23) Polo, E.; Barbieri, A.; Traverso, O. Eur. J. Inorg. Chem. 2003,
324.

3428 Organometallics, Vol. 29, No. 15, 2010
Chen et al.
Found: C, 63.69; H, 3.70; N, 3.38. 1H NMR (300 MHz, CDCl3):
δ 8.54 (d, J = 4.1 Hz, 2H, Py-H), 7.61 (m, 2H, Py-H), 7.34-7.19
(m, 20H, Py-H and Ph-H), 7.16 (m, 2H, Ph-H), 7.00 (d, J = 7.9
Hz, 2H, Ph-H), 5.69 (s, 4H, Cp-H). IR (νCO, cm-1): 1971(s),
1930(s), 1785(s).
3.44 (d, J = 7.8 Hz, 1H, Py-CH2). IR (νCO, cm-1): 1983(s),
1937(s), 1917(s), 1872(s).
Complex 15: orange crystals, yield 60%, mp 139 °C (dec).
Anal. Calcd for C23H15NO7Ru2: C, 44.59; H, 2.44; N, 2.26.
Found: C, 44.80; H, 2.89; N, 2.58. 1H NMR (CDCl3): δ 8.34 (d,
J = 5.0 Hz, 1H, Py-H), [7.76 (m, 1H), 7.58 (t, J = 7.8, 2H), 7.36
(d, J = 7.8 Hz, 1H), 7.30-7.23 (m, 1H), 7.16 (m, 1H), 7.08 (m,
1H)] (Py-H and Ar-H), 5.11 (s, 1H, Cp-H), 3.74 (s, 3H, Me),
3.10-2.89 (m, 3H, Ru-CH and CO-CH2). IR (νCO, cm-1):
2053(s), 1995(s), 1975(s), 1954(s), 1903(s), 1729(m).
Reaction of 1 with 2-Phenylpyridine. Using a procedure similar
to that described above, reaction of 0.10 g (0.13 mmol) of 1 with
0.15 g (0.97 mmol) of 2-phenylpyridine in 30 mL of heptane gave
0.12 g (66% based on Ru) of 9 as yellow crystals. Mp: 180 °C
(dec). Anal. Calcd for C24H16N2O2Ru: C, 61.93; H, 3.46; N,
1
Complex 16: orange crystals, yield 23%, mp 150 °C (dec).
Anal. Calcd for C25H21NO7Ru2: C, 46.23; H, 3.26; N, 2.16.
Found: C, 46.32; H, 3.10; N, 2.31. 1H NMR (CDCl3): δ 8.94 (d,
J = 5.2 Hz, 1H, Py-H), [7.80 (t, J = 7.7 Hz, 1H), 7.70 (d, J = 8.4
Hz, 1H), 7.57 (d, J = 7.7 Hz, 1H), 7.32-7.24 (m, 1H), 7.19 (t,
J = 6.1 Hz, 1H), 7.06 (t, 1H), 6.94 (d, J = 7.7 Hz, 1H)] (Py-H
and Ar-H), 5.40 (s, 1H, Cp-H), 3.73 (s, 3H, Me), 3.56 (s, 3H,
Me), 3.41 (t, J = 7.9 Hz 1H, Ru-CH), 2.98-2.79 (m, 2H, CO-
CH2), [2.01 (d, J = 10.2 Hz, 1H), 1.25-1.09 (m, 2H)] (η2-
CHCH2). IR (νCO, cm-1): 2002(s), 1930(s), 1886(s), 1728(m).
Complex 17: orange crystals, yield 52%, mp 149 °C (dec).
Anal. Calcd for C24H17NO7Ru2: C, 45.50; H, 2.70; N, 2.21.
Found: C, 45.80; H, 2.79; N, 2.38. 1H NMR (400 MHz, CDCl3):
δ 8.29 (d, J = 5.4 Hz, 1H, Py-H), 7.75 (m, 1H, Py-H), 7.61 (d,
J = 8.3 Hz, 1H, Py-H), 7.55 (d, J = 7.7 Hz, 1H, Py-H), 7.36 (d,
J = 8.4 Hz, 1H, Ar-H), 7.27 (m, 1H, Ar-H), 7.18 (t, J = 7.8,
7.2 Hz, 1H, Ar-H), 7.06 (t, J = 6.05 Hz, 1H, Ar-H), 5.01 (s, 1H,
Cp-H), 3.82 (s, 3H, Me), 2.83 (m, 1H, Me-CH), 2.75 (d, J = 11.4
Hz, 1H, Ru-CH), 1.49 (d, J = 6.3 Hz, 3H, Me). IR (νCO, cm-1):
2063(s), 2005(s), 1980(s), 1947(s), 1897(s), 1730(m).
6.02. Found: C, 62.36; H, 3.66, N, 5.91. H NMR (400 MHz,
CDCl3): δ 9.05 (d, J = 5.1 Hz, 1H, Py-H), 8.07 (d, J = 7.4 Hz,
1H, Py-H), 7.98 (d, J = 8.1 Hz, 1H, Py-H), 7.90 (m, 1H, Py-H),
7.83-7.73 (m, 2H, Py-H), 7.65 (d, J = 7.6 Hz, 1H, Py-H), 7.55
(m, 1H, Py-H), 7.31-7.21 (m, 3H, Ph-H), 7.13 (m, 1H, Ph-H),
6.92 (m, 1H, Ph-H), 6.83 (m, 1H, Ph-H), 6.78-6.71 (m, 2H, Ph-
H). IR (νCO, cm-1): 2003(s), 1940(s).
Reaction of 1 with PPh3. Using a procedure similar to that
described above, reaction of 0.096 g (0.13 mmol) of 1 with 0.040 g
(0.15 mmol) of PPh3 in 15 mL of toluene under reflux for 20 h
gave 0.065 g (52%) of 10 as orange crystals. Mp: 150 °C (dec).
Anal. Calcd for C40H24NO8PRu3: C, 48.98; H, 2.47; N, 1.43.
Found: C, 49.04; H, 2.55; N, 1.53. 1H NMR (400 MHz, CDCl3):
δ 8.12 (d, J = 5.3 Hz, 1H, Py-H), 7.70 (d, J = 7.9 Hz, 1H, Py-H),
7.51 (d, J = 8.1 Hz, 1H, Py-H), 7.50-7.39 (m, 3H, Py-H and Ar-
H), 7.29-7.10 (m, 16H, Ar-H), 6.58 (t, J = 6.4, 6.9 Hz, 1H, Ar-
H), 5.42 (s, 1H, Cp-H). 31P NMR (400 MHz, CDCl3): δ -26.85
(s). IR (νCO, cm-1): 2060(s), 2001(s), 1986(s), 1970(s), 1959(s),
1936(s), 1919(s).
General Procedure for the Reactions of 1 with Alkenes. A solu-
tion of 0.20 g (0.27 mmol) of 1 and 1.4 mmol of alkenes in 20 mL
of toluene was refluxed for 20 h. The solvent was removed under
reduced pressure, and the residue was placed in an Al2O3 column.
Elution with CH2Cl2/petroleum ether gave the products.
Complex 11: yellow crystals, yield 50%, mp 145 °C (dec).
Anal. Calcd for C27H17NO5Ru2: C, 50.86; H, 2.69; N, 2.20.
Found: C, 50.55; H, 2.80; N, 2.30. 1H NMR (CDCl3): δ 8.27 (d,
J = 5.0 Hz, 1H, Py-H), [7.74 (m, 1H), 7.60 (d, J = 8.3 Hz, 1H),
7.54 (d, J = 7.6 Hz, 1H), 7.42-7.12 (m, 8H), 7.05 (m, 1H)] (Py-H
and Ar-H), 5.22 (s, 1H, Cp-H), 3.48 (dd, J = 14.2, 6.8 Hz, 1H,
Ph-CH2), 3.14 (dd, J = 14.2, 6.8 Hz, 1H, Ph-CH2), 3.02 (t, J =
7.2 Hz, 1H, Ru-CH). IR (νCO, cm-1): 2053(s), 1997(s), 1981(s),
1947(s), 1891(s).
Complex 12: yellow oil, yield 31%. Anal. Calcd for C31H33-
NO5Ru2: C, 53.06; H, 4.74; N, 2.00. Found: C, 53.36; H, 4.52; N,
1.95. 1H NMR (CDCl3): δ 8.34 (d, J = 5.4 Hz, 1H, Py-H), [7.74
(t, J = 7.8 Hz, 1H), 7.60 (d, J = 8.3 Hz, 1H), 7.53 (d, J = 7.8 Hz,
1H), 7.36 (d, J = 8.3 Hz, 1H), 7.25 (m, 1H), 7.16 (t, J = 7.8 Hz,
1H), 7.06 (t, J = 6.3 Hz, 1H)] (Py-H and Ar-H), 5.10 (s, 1H,
Cp-H), 2.72 (t, J = 7.4 Hz, 1H, Ru-CH), 2.05-1.92 (m, 2H,
CH2), 1.70-1.55 (m, 2H, CH2), 1.26 (s, 16H, CH2), 0.87 (t,
J = 6.9 Hz, 3H, CH3). IR (νCO, cm-1): 2059(s), 1996(s), 1979(s),
1958(s), 1905(s).
Reaction of 1 with Ethoxyethene. Using a similar procedure to
that described above, reaction of 0.20 g (0.27 mmol) of 1 with
0.20 g (2.8 mmol) of ethoxyethene in 20 mL of toluene gave 0.090 g
(60%) of 13, 0.020 g (12%) of 18a, and 0.020 g (12%) of 18b as
orange crystals. The following are data for 18a. Mp: 125 °C
(dec). Anal. Calcd for C25H19NO6Ru2: C, 47.54; H, 3.03; N,
1
2.22. Found: C, 47.10; H, 3.35; N, 2.53. H NMR (CDCl3): δ
8.38 (d, J = 5.5 Hz, 1H, Py-H), [7.93 (d, J = 8.3 Hz, 1H), 7.72
(m, 1H), 7.51 (d, J = 7.9 Hz, 1H), 7.36 (d, J = 8.3 Hz, 1H), 7.24
(m, 1H), 7.15 (m, 1H), 7.05 (m, 1H)] (Py-H and Ar-H), [4.61 (m,
1H), 3.89 (m, 1H), 3.65 (m, 1H), 3.25 (d, J = 5.1 Hz, 1H), 2.57--
2.43 (m, 1H), 2.37-2.19 (m, 2H), 1.67-1.56 (m, 1H)] (Ru-CH
and -CH2), 1.35 (t, J = 7.0 Hz, 3H, Me). IR (νCO, cm-1):
2064(s), 2003(s), 1962(s), 1952(s), 1897(s). The following are
data for 18b. Mp: 114 °C (dec). Anal. Calcd for C25H19NO6Ru2:
C, 47.54; H, 3.03; N, 2.22. Found: C, 47.60; H, 3.35; N, 2.30. 1H
NMR (CDCl3): δ 8.40 (d, J = 4.8 Hz, 1H, Py-H), [7.78-7.67 (m,
2H), 7.49 (d, J = 8.0 Hz, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7.30-
7.16 (m, 2H), 7.07 (m, 1H)) (Py-H and Ar-H), [4.66 (s, 1H),
3.84-3.61 (m, 2H), 3.47 (d, J = 4.0 Hz, 1H), 2.83-2.67 (m, 1H),
2.24-2.02 (m, 2H), 1.85-1.71 (m, 1H)] (Ru-CH and -CH2), 1.27
(t, J = 6.8 Hz, 3H, Me). IR (νCO, cm-1): 2061(s), 2002(s),
1985(s), 1966(s), 1903(s).
Complex 13: orange crystals, yield 20%, mp 130 °C (dec).
Anal. Calcd for C21H13NO5Ru2: C, 44.92; H, 2.33; N, 2.49.
Found: C, 45.38; H, 2.40; N, 2.65. 1H NMR (CDCl3): δ 8.35 (m,
1H, Py-H), [7.79-7.69 (m, 1H), 7.61 (d, J = 8.2 Hz, 1H), 7.53 (t,
J = 7.4 Hz, 1H), 7.36 (m, 1H), 7.28-7.22 (m, 1H), 7.16 (m, 1H),
7.05 (m, 1H)] (Py-H and Ar-H), [5.14 (s), 5.00 (s)] (total 1H, Cp-
H), [2.79 (q), 2.59 (q)] (total 1H, Ru-CH), [1.78 (d, J = 7.0 Hz),
1.34 (d, J = 7.0 Hz)] (total 3H, Me). IR (νCO, cm-1): 2062(s),
2004(s), 1984(s), 1955(s), 1901(s).
Complex 14: orange crystals, yield 58%, mp 160 °C (dec).
Anal. Calcd for C25H16N2O4Ru2: C, 49.18; H, 2.64; N, 4.59.
Found: C, 49.21; H, 2.40; N, 4.82. 1H NMR (CDCl3): δ 8.39 (d,
J = 5.3 Hz, 1H, Py-H), 8.23 (d, J = 5.6 Hz, 1H, Py-H),
[7.55-7.43 (m, 3H), 7.31 (d, J = 7.6 Hz, 1H), 7.28-7.22 (m,
2H), 7.15 (t, J = 7.6 Hz, 1H), 7.04 (t, J = 7.3 Hz, 1H), 6.87-6.77
(m, 2H)] (Py-H and Ar-H), 4.47 (s, 1H, Cp-H), 4.02 (dd, J =
18.3, 7.8 Hz, 1H, Ru-CH), 3.84 (d, J = 18.3 Hz, 1H, Py-CH2),
Reaction of 1 with Norbornene. A solution of 0.20 g (0.27
mmol) of 1 and 0.13 g (1.4 mmol) of norbornene in 20 mL of
toluene was refluxed for 25 h. The solvent was removed under
reduced pressure, and the residue was placed in an Al2O3
column. Elution with CH2Cl2/petroleum ether gave 19 (0.030 g,
18%) as a yellow solid, in addition to 4 (0.010 g, 5%). 19: mp
132 °C (dec). Anal. Calcd for C26H19NO5Ru2: C, 49.76; H, 3.05;
N, 2.23. Found: C, 49.78; H, 2.80; N, 2.27. 1H NMR (CDCl3): δ
8.19 (d, J = 5.5 Hz, 1H, Py-H), [7.73 (m, 1H), 7.62 (d, J = 8.4
Hz, 1H), 7.49 (d, J = 7.7 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H),
7.31-7.24 (m, 1H), 7.18 (t, J = 7.7 Hz, 1H), 7.06 (m, 1H)] (Py-H
and Ar-H), 4.86 (s, 1H, Cp-H), [2.43-2.15 (m, 4H), 1.98-1.92
(m, 1H), 1.65-0.83 (m, 5H)] (norbornyl ring-H). IR (νCO
,
cm-1): 2061(s), 1996(s), 1973(s), 1954(s), 1895(s).
Reaction of 1 with Cyclohexene. Using a similar procedure to
that described above, reaction of 1 (0.20 g, 0.27 mmol) with
cyclohexene (0.11 g, 1.3 mmol) gave 20 (0.012 g, 7%) as a yellow

Article
Organometallics, Vol. 29, No. 15, 2010 3429
Table 2. Crystal Data and Summary of X-ray Data Collection
1
2
3
4
5
8
formula
fw
T, K
λ, A
cryst syst
C23H9NO9Ru3
746.52
294(2)
0.71073
triclinic
P1
9.3755(14)
11.0167(17)
12.1641(19)
87.708(2)
74.862(2)
78.775(2)
1189.5(3)
2
C33H27N2O2Ru
584.64
294(2)
0.71073
triclinic
P1
10.260(2)
11.254(2)
11.605(2)
88.589(3)
87.410(3)
79.701(4)
1316.9(4)
2
C32H19N2O4Ru2
697.63
294(2)
0.71073
monoclinic
P21/n
9.7603(13)
17.940(3)
15.399(2)
90
94.397(3)
90
2688.3(6)
4
1.724
1.165
1380
C21H9NO7Ru3
690.50
294(2)
0.71073
triclinic
P1
7.1276(14)
9.6244(19)
16.457(3)
104.779(3)
97.070(3)
103.930(3)
1038.8(4)
2
C30H20N2O2Ru
541.55
113(2)
0.71073
monoclinic
P21/c
14.857(3)
8.9139(18)
18.954(4)
90
112.26(3)
90
2323.1(8)
4
1.548
0.706
1096
C24H16NO2Ru
451.45
294(2)
0.71073
monoclinic
C2/c
16.451(3)
14.350(2)
17.250(3)
90
112.454(3)
90
3763.5(10)
8
1.594
0.853
1816
˚
space group
˚
a, A
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
3
˚
V, A
Z
Dcalc, g cm-3
2.084
1.934
716
1.474
0.629
598
2.208
2.198
660
3
μ, mm-1
F(000)
cryst size, mm
θ range, deg
no. of reflns collected
0.28 ꢀ 0.24 ꢀ 0.20 0.20 ꢀ 0.14 ꢀ 0.12 0.14 ꢀ 0.10 ꢀ 0.10 0.20 ꢀ 0.16 ꢀ 0.10 0.14 ꢀ 0.12 ꢀ 0.08 0.22 ꢀ 0.22 ꢀ 0.10
2.29-25.01
6025
1.76-25.01
6684
1.75-26.46
14 997
1.31-25.02
5427
2.23-25.02
13 011
1.95-26.40
10 713
no. of indep reflns/Rint 4166/0.0194
4615/0.0176
344
1.086
0.0326/0.0780
0.0446/0.0844
0.609, -0.325
5522/0.0609
361
0.992
0.0416/0.0787
0.0922/0.0947
1.373, -0.439
3654/0.0213
289
1.021
0.0247/0.0488
0.0347/0.0520
0.387, -0.569
4092/0.0360
316
1.051
0.0276, 0.0690
0.0315, 0.0713
0.480, -0.430
3858/0.0437
253
1.003
0.0328, 0.0666
0.0581, 0.0751
0.419, -0.382
no. of params
325
1.124
0.0262/0.0645
0.0329/0.0699
0.398, -0.915
goodness-of-fit on F2
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
largest diff peak
-3
˚
and hole, e A
9
10
11
13
14
formula
fw
T, K
λ, A
cryst syst
C24H16N2O2Ru
465.46
294(2)
0.71073
monoclinic
P21/c
9.0164(17)
13.376(3)
16.487(3)
90
97.947(3)
90
1969.3(7)
4
1.570
0.819
936
C40H24NO8PRu3
980.78
113(2)
0.71073
monoclinic
P21/n
10.107(2)
22.630(5)
15.899(3)
90
100.26(3)
90
3578.2(12)
4
1.821
1.351
1928
C27H17O5Ru2
637.56
113(2)
0.71070
monoclinic
P21/c
8.8321(9)
17.6060(14)
15.6816(14)
90
94.609(5)
90
2430.6(4)
4
1.742
1.281
1256
C21H13NO5Ru2
561.46
294(2)
0.71073
triclinic
P1
9.0160(19)
9.2492(19)
13.378(3)
70.030(3)
79.719(3)
73.811(3)
1002.7(4)
2
C25H16N2O4Ru2
610.54
294(2)
0.71073
monoclinic
P21/n
9.4777(13)
15.288(2)
16.231(2)
90
106.233(2)
90
2258.0(5)
4
1.796
1.372
1200
˚
space group
˚
a, A
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
3
˚
V, A
Z
Dcalc, g cm-3
1.860
1.538
548
3
μ, mm-1
F(000)
cryst size, mm
θ range, deg
0.24 ꢀ 0.16 ꢀ 0.14
1.97-25.02
9853
3477/0.0362
262
1.020
0.0377, 0.0864
0.0679, 0.1020
0.606, -0.311
0.18 ꢀ 0.16 ꢀ 0.12
2.24-25.02
20 062
6272/0.0330
478
1.132
0.0234, 0.0593
0.0255, 0.0604
0.473, -0.711
0.22 ꢀ 0.18 ꢀ 0.16
1.74-27.80
22 458
5720/0.0555
317
1.125
0.0629/0.1126
0.0745/0.1184
1.968, -1.933
0.22 ꢀ 0.16 ꢀ 0.14
1.63-26.45
5791
4057/0.0174
262
0.932
0.0486/0.1244
0.0813/0.1521
1.799, -1.644
0.30 ꢀ 0.26 ꢀ 0.22
1.87-25.01
11 394
3977/0.0279
298
1.051
0.0231/0.0517
0.0363/0.0575
0.391, -0.283
no. of reflns collected
no. of indep reflns/Rint
no. of params
goodness-of-fit on F2
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
largest diff peak
-3
˚
and hole, e A
15
16
18a
18b
21
formula
fw
T, K
λ, A
cryst syst
C23H15NO7Ru2
619.50
113(2)
0.71070
monoclinic
P21/c
9.894(4)
13.510(5)
17.462(7)
90
103.870(4)
90
C25H21NO7Ru2
649.57
294(2)
0.71073
triclinic
P1
10.344(3)
11.453(3)
11.747(4)
66.805(4)
66.350(5)
74.733(4)
1162.6(6)
2
C25H19NO6Ru2
631.55
293(2)
0.71070
orthorhombic
P212121
10.174(3)
13.461(4)
17.460(6)
90
C25H19NO6Ru2
631.55
113(2)
0.71070
monoclinic
P21/c
8.503(5)
24.246(12)
11.983(6)
90
108.543(5)
90
C31H21NO5Ru2
689.63
293(2)
0.71070
monoclinic
P21/n
9.6179(7)
20.5240(13)
13.7341(9)
90
100.302(3)
90
˚
space group
˚
a, A
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
90
90
3
˚
V, A
Z
2266.1(15)
4
1.816
2391.3(13)
4
1.754
2342(2)
4
1.791
2667.4(3)
4
1.717
Dcalc, g cm-3
1.856
1.347
3
μ, mm-1
1.377
1.304
1.331
1.174

3430 Organometallics, Vol. 29, No. 15, 2010
Chen et al.
Table 2. Continued
16
15
18a
18b
21
F(000)
cryst size, mm
θ range, deg
1216
644
1248
1248
1368
0.14 ꢀ 0.12 ꢀ 0.12
1.93-27.88
20 620
5370/0.0249
300
1.040
0.0231/0.0487
0.0265/0.0502
0.657, -0.458
0.22 ꢀ 0.16 ꢀ 0.12
1.95-25.02
6055
4076/0.0181
316
0.778
0.0242/0.0625
0.0341/0.0738
0.377, -0.422
0.22 ꢀ 0.20 ꢀ 0.16
2.32-27.88
22 250
5695/0.0372
309
1.029
0.0231/0.0460
0.0256/0.0467
0.349, -0.329
0.16 ꢀ 0.14 ꢀ 0.14
1.68-27.89
21 492
5531/0.0380
309
1.106
0.0385/0.0859
0.0445/0.0909
1.166, -0.820
0.20 ꢀ 0.20 ꢀ 0.20
1.80-27.87
20 497
6328/0.0542
355
1.093
0.0526/0.0933
0.0698/0.1012
0.883, -0.641
no. of reflns collected
no. of indep reflns/Rint
no. of params
goodness-of-fit on F2
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
largest diff peak
-3
˚
and hole, e A
solid and 4 (0.015 g, 8%). 20: mp 118 °C (dec). Anal. Calcd for
C25H19NO5Ru2: C, 48.78; H, 3.11; N, 2.28. Found: C, 49.10; H,
2.78; N, 2.27. 1H NMR (CDCl3): δ 8.28 (d, J = 5.5 Hz, 1H, Py-
H), [7.73 (m, 1H), 7.62 (d, J = 8.3 Hz, 1H), 7.53 (d, J = 7.8 Hz,
1H), 7.40 (d, J = 8.3 Hz, 1H), 7.30-7.25 (m, 1H), 7.18 (m, 1H),
7.04 (m, 1H)] (Py-H and Ar-H), 5.09 (s, 1H, Cp-H), [2.27-2.21
(m, 2H), 2.02-1.93 (m, 2H), 1.73-1.21 (m, 6H)] (cyclohexyl
ring-H). IR (νCO, cm-1): 2061(s), 2007(s), 1980(s), 1967(s),
1902(s).
0.27 mmol) with 2,3,4,5-tetramethylcyclopent-2-enone (0.19 g,
1.4 mmol) only gave 0.025 g of 4 in 14% yield.
Catalytic Reaction of 3-(2-Pyridyl)indene with Styrene. A
solution of 0.19 g (1.0 mmol) of 3-(2-pyridyl)indene, 0.52 g
(5.0 mmol) of styrene, and 0.038 g (0.06 mmol) of Ru3(CO)12 in
5 mL of toluene was refluxed for 20 h. The solvent and styrene
were removed under reduced pressure, and the residue was
placed in an Al2O3 column. Elution with CH2Cl2/petroleum
ether developed 0.025 g of complex 2 (26%) and 0.14 g of 3-(2-
pyridyl)indene (recovery yield: 74%).
Reaction of 1 with 6,60-Dimethylbenzofulvene. Using a similar
procedure to that described above, reaction of 1 (0.20 g,
0.27 mmol) with 6,60-dimethylbenzofulvene (0.21 g, 1.3 mmol)
gave 21 (0.008 g, 7%) as yellow crystals and 4 (0.005 g, 3%). 21:
mp 171 °C (dec). Anal. Calcd for C31H21NO5Ru2: C, 53.99; H,
3.07; N, 2.03. Found: C, 53.60; H, 3.36; N, 1.77. 1H NMR
(CDCl3): δ 8.37 (d, J = 5.4 Hz, 1H, Py-H), [7.92 (m, 1H), 7.71 (d,
J = 7.8 Hz, 1H), 7.61 (d, J = 8.4 Hz, 1H), 7.54-7.48 (m, 3H),
7.43 (d, J = 8.4 Hz, 1H), 7.33-7.17 (m, 4H)] (Py-H and Ar-H),
5.64 (s, 1H, Cp-H), 5.62 (s, 1H, Cp-H), 3.00 (m, 1H, Me2-CH),
1.17 (d, J = 6.8 Hz, 3H, Me), 1.11 (d, J = 6.8 Hz, 3H, Me). IR
(νCO, cm-1): 2068(s), 2015(s), 1980(s), 1959(s), 1901(s).
Reaction of 1 with (E)-2-Hexene. Using a similar procedure to
that described above, reaction of 1 (0.20 g, 0.27 mmol) with (E)-
2-hexene (0.11 g, 1.3 mmol) gave 22 (0.035 g, 21%) as a yellow
solid and 4 (0.020 g, 11%). 22: mp 54-55 °C. Anal. Calcd for
C25H21NO5Ru2: C, 48.62; H, 3.43; N, 2.27. Found: C, 49.00; H,
3.60; N, 2.53. 1H NMR (CDCl3): δ 8.34 (d, J = 5.6 Hz, 1H, Py-
H), [7.73 (m, 1H), 7.60 (d, J = 8.4 Hz, 1H), 7.53 (d, J = 7.7 Hz,
1H), 7.36 (d, J = 8.4 Hz, 1H), 7.28-7.22 (m, 1H), 7.15 (m, 1H),
7.06 (m, 1H)] (Py-H and Ar-H), 5.10 (s, 1H, Cp-H), 2.73 (t, J =
7.4 Hz, 1H, Ru-CH), 2.06-1.23 (m, 8H, CH2), 0.91 (t, J =
7.2 Hz, 3H, Me). IR (νCO, cm-1): 2063(s), 2024(m), 1998(s),
1979(s), 1908(s).
Crystallographic Studies. Single crystals of complexes 1-5,
8-11, 13-16, 18a, 18b, and 21 suitable for X-ray diffraction
were obtained from hexane/CH2Cl2 solution. Data collection
was performed on a Bruker Smart 1000 (for 1-4, 8, 9, 13, 14,
and 16) or a Rigaku MM-OO7/Saturn 70 (for 5, 10, 11, 15, 18a,
18b, and 21) diffractometer, using graphite-monochromated
Mo KR radiation (ω-2θ scans). Semiempirical absorption
corrections were applied for all complexes. The structures were
solved by direct methods and refined by full-matrix least-
squares. All calculations were done using the SHELXL-97
program system. The crystal data and summary of X-ray data
collection are listed in Table 2.
Acknowledgment. We thank Dr. Yongqiang Zhang for
his help in revising this paper. We also thank the National
Natural Science Foundation of China (Nos. 20872066
and 20721062) and the Research Fund for the Doctoral
Program of Higher Education of China (No. 20070055020)
for financial support.
Supporting Information Available: Crystallographic details
for 1-5, 8-11, 13-16, 18a, 18b, and 21 in CIF format are pro-
vided. This material is available free of charge via the Internet at
http://pubs.acs.org.
Reaction of 1 with 2,3,4,5-Tetramethylcyclopent-2-enone. Using
a similar procedure to that described above, reaction of 1 (0.20 g,