Reactions of a trinuclear ruthenium complex derived from 3-(2-Pyridyl)indene with diphenylacetylene and phenylacetylene: Insertion of alkynes into the Ru-C bond

Article abstract of DOI:10.1021/om1008007

Thermal treatment of the trinuclear ruthenium complex {μ₂- η⁵:η¹-(C₅H₄N)(C ₉H₅)}Ru₃(CO)₉ (1) with 1 equiv of diphenylacetylene gave the trinuclear complex {μ₃- η¹:η²:η⁵-(C₅H ₄N)(C₉H₅)(PhC-CPh)}Ru₃(CO) ₇ (2) via the insertion of an alkyne into the Ru-C(η¹) bond of 1. Complex 2 could be transformed into the dinuclear and trinuclear complexes {μ₂-η¹:η⁵-(C ₅H₄N)(C₉H₅)(PhC-CPh)}Ru ₂(CO)₂(μ₂-η²: η⁴-CPh-CPhCPh-CPh) (3), {μ₃-η²: η³:η⁵-(C₅H₄N)(C ₉H₅)(CPhCPh-CPhCPh)}Ru₃(CO)₆ (4), and {μ₂-η¹:η⁵-(C₅H ₄N)(C₉H₅)(PhC-CPh)}Ru₃(CO) ₄(μ₃-η²-PhC-CPh)₂ (5) in the presence of excess diphenylacetylene. Similarly, reaction of 1 with 1 equiv of phenylacetylene gave the alkyne-inserted product {μ₃- η¹:η²:η⁵-(C₅H ₄N)(C₉H₅)(HC-CPh)}Ru₃(CO) ₇ (6), which could also react with excess phenylacetylene to give the complexes {μ₃-η²:η⁴: η⁵-(C₅H₄N)(C₉H ₅)(C-CPhCH-CPh)}(μ₂-H)Ru₃(CO)₆ (7) and {μ₂-η²:η⁴-(C ₅H₄N)(C₉H₆)(C-CPhCH-CPh)}Ru ₂(CO)₄(μ₂-CO) (8). Complex 7 could be transformed slowly into 8 in refluxing toluene. The reactions of 3-(2-pyridyl)indene with internal alkynes catalyzed by Ru₃(CO) ₁₂ and 1 were also tested, obtaining several C-H/alkyne coupling products, while the reaction with phenylacetylene did not work under the same conditions. The molecular structures of 2-8 were determined by X-ray diffraction.

Full text of DOI:10.1021/om1008007

676 Organometallics 2011, 30, 676–683
DOI: 10.1021/om1008007
Reactions of a Trinuclear Ruthenium Complex Derived from
3-(2-Pyridyl)indene with Diphenylacetylene and Phenylacetylene:
Insertion of Alkynes into the Ru-C bond
Dafa Chen,† Congying 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 August 17, 2010
Thermal treatment of the trinuclear ruthenium complex {μ2-η5:η1-(C5H4N)(C9H5)}Ru3(CO)9 (1)
with 1 equiv of diphenylacetylene gave the trinuclear complex {μ3-η1:η2:η5-(C5H4N)(C9H5)(PhCd
CPh)}Ru3(CO)7 (2) via the insertion of an alkyne into the Ru-C(η1) bond of 1. Complex 2 could be
transformed into the dinuclear and trinuclear complexes {μ2-η1:η5-(C5H4N)(C9H5)(PhCdCPh)}
Ru2(CO)2(μ2-η2:η4-CPhdCPhCPhdCPh) (3), {μ3-η2:η3:η5-(C5H4N)(C9H5)(CPhCPhdCPhCPh)}
Ru3(CO)6 (4), and {μ2-η1:η5-(C5H4N)(C9H5)(PhCdCPh)}Ru3(CO)4(μ3-η2-PhCdCPh)2 (5) in the
presence of excess diphenylacetylene. Similarly, reaction of 1 with 1 equiv of phenylacetylene gave the
alkyne-inserted product {μ3-η1:η2:η5-(C5H4N)(C9H5)(HCdCPh)}Ru3(CO)7 (6), which could also
react with excess phenylacetylene to give the complexes {μ3-η2:η4:η5-(C5H4N)(C9H5)(CdCPhCHdCPh)}
(μ2-H)Ru3(CO)6 (7) and {μ2-η2:η4-(C5H4N)(C9H6)(CdCPhCHdCPh)}Ru2(CO)4(μ2-CO) (8). Com-
plex 7 could be transformed slowly into 8 in refluxing toluene. The reactions of 3-(2-pyridyl)indene
with internal alkynes catalyzed by Ru3(CO)12 and 1 were also tested, obtaining several C-H/alkyne
coupling products, while the reaction with phenylacetylene did not work under the same conditions.
The molecular structures of 2-8 were determined by X-ray diffraction.
Introduction
reactions with diphenylacetylene and phenylacetylene. On
the basis of the different reaction results, we wish to get some
useful information to understand the different reactivity
between internal alkynes and terminal alkynes in chelation-
assisted C-H/alkyne coupling reactions.
As a green and atom-economical method, C-C coupling
through C-H bond activation by transition-metal com-
plexes has been developing rapidly in recent years.1 For
example, functional group directed aromatic C-H/alkyne
coupling is an effective method not only to introduce olefinic
groups to the ortho position of an aromatic ring but also to
synthesize various heterocycles.1a-e,2-5 However, in some
cases, terminal alkynes were not suitable, partly because of
their oligomerization.5 We have recently reported the reac-
tions of the trinuclear complex {μ2-η5:η1-(C5H4N)(C9H5)}Ru3-
(CO)9 (1), derived from 3-(2-pyridyl)indene, with alkenes,
giving a series of C-C coupling products via 1,1-insertion of
alkenes into the Ru-C(η1) bond.6 Here we further report its
Results and Discussion
Reaction of 1 with Diphenylacetylene. When the complex
{μ2-η5:η1-(C5H4N)(C9H5)}Ru3(CO)9 (1) reacted with 1 equiv
of diphenylacetylene in refluxing toluene, the complex {μ3-
η1:η2:η5-(C5H4N)(C9H5)(PhCdCPh)}Ru3(CO)7 (2) was
(2) (a) Halbritter, G.; Knoch, F.; Wolski, A.; Kisch, H. Angew.
Chem., Int. Ed. 1994, 33, 1603. (b) Aulwurm, U. R.; Melchinger, J. U.;
Kisch, H. Organometallics 1995, 14, 3385. (c) Kakiuchi, F.; Sato, T.;
Tsujimoto, T.; Yamauchi, M.; Chatani, N.; Murai, S. Chem. Lett. 1998,
27, 1053. (d) Lim, S.-G.; Lee, J. H.; Moon, C. W.; Hong, J.-B.; Jun, C.-H.
Org. Lett. 2003, 5, 2759. (e) Kuninobu, Y.; Kawata, A.; Takai, K. J. Am.
Chem. Soc. 2005, 127, 13498. (f) Kuninobu, Y.; Tokunaga, Y.; Kawata,
A.; Takai, K. J. Am. Chem. Soc. 2006, 128, 202. (g) Umeda, N.; Tsurugi,
H.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2008, 47, 4019. (h) Li,
L.; Brennessel, W. W.; Jones, W. D. J. Am. Chem. Soc. 2008, 130, 12414.
(i) Parthasarathy, K.; Jeganmohan, M.; Cheng, C.-H. Org. Lett. 2008,
10, 325. (j) Katagiri, T.; Mukai, T.; Satoh, T.; Hirano, K.; Miura, M.
Chem. Lett. 2009, 38, 118. (k) Guimond, N.; Fagnou, K. J. Am. Chem.
Soc. 2009, 131, 12050. (l) Gao, K.; Lee, P.-S.; Fujita, T.; Yoshikai, N. J.
Am. Chem. Soc. 2010, 132, 12249. (m) Ding, S.; Shi, Z.; Jiao, N. Org.
Lett. 2010, 12, 1540. (n) Chen, J.; Song, G.; Pan, C.-L.; Li, X. Org. Lett.
2010, 12, 5426. (o) Too, P. C.; Wang, Y.-F.; Chiba, S. Org. Lett. 2010, 12,
5688.
*To whom correspondence should be addressed. Fax: þ86-22-
23504781. E-mail: bqwang@nankai.edu.cn.
(1) For recent reviews, see: (a) Ritleng, V.; Sirlin, C.; Pfeffer, M.
Chem. Rev. 2002, 102, 1731. (b) Kakiuchi, F.; Chatani, N. Adv. Synth.
Catal. 2003, 345, 1077. (c) Dyker, G., Handbook of C-H Transforma-
tions. Applications in Organic Synthesis; Wiley-VCH: Weinheim,
Germany, 2005. (d) Horino, Y. Angew. Chem., Int. Ed. 2007, 46, 2144.
(e) Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110,
624. (f) Kakiuchi, F.; Murai, S. Acc. Chem. Res. 2002, 35, 826. (g)
Godula, K.; Sames, D. Science 2006, 312, 67. (h) Alberico, D.; Scott,
M. E.; Lautens, M. Chem. Rev. 2007, 107, 174. (i) Herrerıas, C. I.; Yao,
´
X.; Li, Z.; Li, C.-J. Chem. Rev. 2007, 107, 2546. (j) Campos, K. R. Chem.
Soc. Rev. 2007, 36, 1069. (k) Seregin, I. V.; Gevorgyan, V. Chem. Soc.
Rev. 2007, 36, 1173. (l) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010,
110, 1147.
r
pubs.acs.org/Organometallics
Published on Web 02/04/2011
2011 American Chemical Society

Article
Organometallics, Vol. 30, No. 4, 2011 677
Scheme 1
Figure 1. ORTEP diagram of 2. Thermal ellipsoids are shown
at the 50% probability level. Hydrogen atoms have been
omitted for clarity. Selected bond lengths (A): Ru(1)-N(1) =
2.190(3), Ru(1)-C(28) = 2.266(4), Ru(1)-C(29) = 2.282(4),
Ru(1)-Ru(3)=2.6466(6), Ru(1)-Ru(2)=2.8939(6), Ru(2)-
Ru(3) = 2.8946(6), Ru(3)-C(28) = 2.123(4), C(28)-C(29) =
1.414(5).
corresponding Ru-Ru distance in complex 1 (2.9393(5) A).
This may be caused by the bridging PhCdCPh ligand. The
C(28)-C(29) distance is 1.414(5) A, longer than the value for a
typical CdC double bond (∼1.34 A). The Ru(1)-C(28) and
Ru(1)-C(29) distances (2.266(4), 2.282(4) A) are much long-
er than the Ru(3)-C(28) distance (2.123(4) A) but much
1
obtained in 64% yield (Scheme 1). Its H NMR spectrum
shows five groups of peaks at 8.52-6.70 ppm for the pyridyl
and benzo protons and one singlet at 5.01 ppm for the C5 ring
proton of indenyl. Single-crystal X-ray diffraction analysis
shows that complex 2 is a triruthenium complex (Figure 1),
and the three Ru atoms bond to each other. The Ru(1)-Ru(3)
distance (2.6466(6) A) is much shorter than those of Ru(1)-
Ru(2) and Ru(2)-Ru(3) (2.8939(6), 2.8946(6) A) and the
shorter than the Ru(3) C(29) distance (3.117 A), indicat-
3 3 3
ing that the PhCdCPh ligand coordinates with Ru(1) in
an η2 mode but with Ru(3) in an η1 mode.
A possible formationmechanismof 2 is shownin Scheme 2.
Diphenylacetylene inserts into the Ru-C(η1) bond first,7 and
then the double bond of the PhCdCPh unit coordinates with
a Ru atom to replace a carbonyl. This may promote the
formation of the third Ru-Ru bond and release of a car-
bonyl to give 2a. 2a and 2 might be transformed into each
other under certain conditions.
(3) (a) Kakiuchi, F.; Yamamoto, Y.; Chatani, N.; Murai, S. Chem.
Lett. 1995, 24, 681. (b) Londergan, T. M.; You, Y.; Thompson, M. E.;
Weber, W. P. Macromolecules 1998, 31, 2784. (c) Harris, P. W. R.;
Rickard, C. E. F.; Woodgate, P. D. J. Orgnomet. Chem. 1999, 589, 168.
(d) Kakiuchi, F.; Uetsuhara, T.; Tanaka, Y.; Chatani, N.; Murai, S. J.
Mol. Catal. A 2002, 182-183, 511. (e) Stuart, D. R.; Bertrand-Laperle,
M.; Burgess, K. M. N.; Fagnou, K. J. Am. Chem. Soc. 2008, 130, 16474.
(4) (a) Satoh, T.; Nishinaka, Y.; Miura, M.; Nomura, M. Chem. Lett.
1999, 28, 615. (b) Shibata, Y.; Otake, Y.; Hirano, M.; Tanaka, K. Org.
Lett. 2009, 11, 689. (c) Wu, J.; Cui, X.; Mi, X.; Li, Y.; Wu, Y. Chem.
Commun. 2010, 46, 6771. (d) Cant, A. A.; Roberts, L.; Greaney, M. F.
Chem. Commun. 2010, 46, 8671. (e) Sun, Z.-M.; Chen, S.-P.; Zhao, P.
Chem. Eur. J. 2010, 16, 2619. (f) Satoh, T.; Miura, M. Chem. Eur. J.
2010, 16, 11212and references therein. (g) Guimond, N.; Gouliaras, C.;
Fagnou, K. J. Am. Chem. Soc. 2010, 132, 6908. (h) Schipper, D. J.;
Hutchinson, M.; Fagnou, K. J. Am. Chem. Soc. 2010, 132, 6910. (i)
Rakshit, S.; Patureau, F. W.; Glorius, F. J. Am. Chem. Soc. 2010, 132,
9585. (j) Hyster, T. K.; Rovis, T. J. Am. Chem. Soc. 2010, 132, 10565. (k)
Wang, C.; Rakshit, S.; Glorius, F. J. Am. Chem. Soc. 2010, 132, 14006.
(l) Stuart, D. R.; Alsabeh, P.; Kuhn, M.; Fagnou, K. J. Am. Chem. Soc.
2010, 132, 18326. (m) Morimoto, K.; Hirano, K.; Satoh, T.; Miura, M.
Org. Lett. 2010, 12, 2068. (n) Liu, C.-R.; Yang, F.-L.; Jin, Y.-Z.; Ma
X.-T.; Cheng, D.-J.; Li, N.; Tian, S.-K. Org. Lett. 2010, 12, 3832. (o) Su,
Y.; Zhao, M.; Han, K.; Song, G.; Li, X. Org. Lett. 2010, 12, 5462.
(5) (a) Lim, Y.-G.; Lee, K.-H.; Koo, B. T.; Kang, J.-B. Tetrahedron
Lett. 2001, 42, 7609. (b) Ueura, K.; Satoh, T.; Miura, M. J. Org. Chem.
2007, 72, 5362. (c) Colby, D. A.; Bergman, R. G.; Ellman, J. A. J. Am.
Chem. Soc. 2008, 130, 3645. (d) Mochida, S.; Hirano, K.; Satoh, T.;
Miura, M. J. Org. Chem. 2009, 74, 6295.
Reaction of 2 with Diphenylacetylene. Complex 2 could
further react with excess diphenylacetylene to give the di-
nuclear and trinuclear complexes {μ2-η1:η5-(C5H4N)(C9H5)-
(PhCdCPh)}Ru2(CO)2(μ2-η2:η4-CPhdCPhCPhdCPh) (3),
(7) For some examples of alkyne insertion into Ru-C bonds, see: (a)
Bruce, M.; Gardner, R. C. F.; Stone, F. G. A. J. Chem. Soc., Dalton
Trans. 1976, 81. (b) Bruce, M. I.; Gardner, R. C. F.; Howard, J. A. K.;
Stone, F. G. A.; Welling, M.; Woodward, P. J. Chem. Soc., Dalton
Trans. 1977, 621. (c) Bruce, M. I.; Gardner, R. C. F.; Stone, F. G. A. J.
Chem. Soc., Dalton Trans. 1979, 906. (d) Lutsenko, Z. L.; Aleksandrov,
G. G.; Petrovskii, P. V.; Shubina, E. S.; Andrianov, V. G.; Struchkov,
Yu. T.; Rubezhov, A. Z. J. Organomet. Chem. 1985, 281, 349. (e) Bruce,
M. I.; Catlaw, A.; Cifuentes, M. P.; Snow, M. R.; Tiekink, E. R. T. J.
Organomet. Chem. 1990, 397, 187. (f) Garn, D.; Knoch, F.; Kish, H. J.
Organomet. Chem. 1993, 444, 155. (g) Abbenhuis, H. C. L.; Pfeffer, M.;
Sutter, J. P.; de Cian, A.; Fischer, J.; Li, Ji, H.; Nelson, J. H. Organo-
metallics 1993, 12, 4464. (h) Barns, R. M.; Hubbard, J. L. J. Am. Chem.
Soc. 1994, 116, 9514. (i) Ferstl, W.; Sakodinskaya, I. K.; Beydoun-
Sutter, N.; Le Borgne, G.; Pfeffer, M.; Ryabov, A. D. Organometallics
1997, 16, 411. (j) Ghosh, K.; Pattanayak, S.; Chakravorty, A. Organo-
metallics 1998, 17, 1956. (k) Ghosh, K.; Chattopadhyay, S.; Pattanayak,
S.; Chakravorty, A. Organometallics 2001, 20, 1419. (l) Cabeza, J. A.; del
ꢀ
Rıo, I.; Grepioni, F.; Moreno, M.; Riera, V.; Suarez, M. Organometal-
´
lics 2001, 20, 4190. (m) Boutadla, Y.; Davies, D. L.; Al-Duaij, O.;
Fawcett, J.; Jones, R. C.; Singh, K. Dalton Trans. 2010, 39, 10447. (n)
Davies, D. L.; Al-Duaij, O.; Fawcett, J.; Singh, K. Organometallics 2010,
29, 1413.
(6) Chen, D.; Zhang, X.; Xu, S.; Song, H.; Wang, B. Organometallics
2010, 29, 3418.

678 Organometallics, Vol. 30, No. 4, 2011
Chen et al.
Figure 3. ORTEP diagram of 4. Thermal ellipsoids are shown
at the 30% probability level. Hydrogen atoms have been omitted
for clarity. Selected bond lengths (A): Ru(1)-C(42) = 2.154(6),
Ru(1)-N(1) = 2.174(6), Ru(1)-C(21) = 2.175(6), Ru(1)-
Ru(3) = 2.684(2), Ru(1)-Ru(2) = 2.860(2), Ru(2)-Ru(3) =
2.754(2), Ru(3)-C(42) = 2.029(6), Ru(3)-C(35) = 2.231(6),
Ru(3)-C(28) = 2.431(6), C(21)-C(28) = 1.529(8), C(28)-
C(35) = 1.399(9), C(35)-C(42) = 1.438(9).
Figure 2. ORTEP diagram of 3. Thermal ellipsoids are shown
at the 50% probability level. Hydrogen atoms have been omitted
for clarity. Selected bond lengths (A): Ru(1)-C(21) = 2.063(2),
Ru(1)-C(36) = 2.117(2), Ru(1)-Ru(2) = 2.6649(4), Ru(2)-
C(49) = 2.107(2), Ru(2)-N(1) = 2.120(2), Ru(2)-C(36) =
2.159(2), Ru(2)-C(35) = 2.206(2), Ru(2)-C(21) = 2.310(2),
Ru(2)-C(22) = 2.322(2), C(21)-C(22) = 1.399(3), C(22)-C
(35) = 1.462(3), C(35)-C(36) = 1.427(3), C(49)-C(50)
1.354(3).
=
coupled with a ruthenium atom to from the ruthenacyclo-
pentadiene,8 which is bonded to another ruthenium atom
(Ru(2)) in an η5 mode (Figure 2). However, the five-mem-
bered ring is slightly puckered, with Ru(1) bending away
from the C(21)-C(22)-C(35)-C(36) plane (the dihedral
angle between the C(21)-C(22)-C(35)-C(36) and C(21)-
Ru(1)-C(36) planes is 8.5°). The Ru(1)-Ru(2) distance
(2.6649(4) A) is within the Ru-Ru bond lengths found
previously.8 The C(21)dC(22) and C(35)dC(36) bonds
(1.399(3), 1.427 A) in the π-coordinated bridging PhC(21)d
C(22)Ph-PhC(35)dC(36)Ph ligand are much longer than the
C(49)dC(50) bond (1.354(3) A) in the noncoordinated bridg-
ing PhC(49)dC(50)Ph ligand.
Scheme 2
Complex 4 is a triruthenium complex incorporating two
diphenylacetylene molecules (Figure 3). The two diphenyla-
cetylene molecules are inserted in succession into the Ru-C
bond to form a five-membered ring, which is bonded with
Ru(3) in a twisted η3 mode, as shown by the C-C and Ru-C
bond lengths (C(21)-C(28) = 1.529(8) A, C(28)-C(35) =
1.399(9) A, C(35)-C(42) = 1.438(9) A; Ru(3)-C(42) =
2.029(6) A, Ru(3)-C(28) = 2.431(6) A, Ru(3)-C(35) =
2.231(6) A). The long distance (3.041 A) between the Ru(3)
and C(21) atoms indicates that they do not bond to each
other. The three Ru atoms bond to each other. The Ru(1)-
Ru(3) distance (2.684(2) A) is comparable to the corre-
sponding Ru-Ru distance in 2 (2.6466(6) A) but is shorter
than the Ru(1)-Ru(2) and Ru(2)-Ru(3) distances (2.860(2),
2.754(2) A). A possible formation mechanism of 4 is shown
in Scheme 3. Complex 2 transforms into 2a first, followed by
diphenylacetylene insertion into the Ru-C(Ph) bond, form-
ing the intermediate {μ3-η1:η4:η5-(C5H4N)(C9H5)(CPhd
CPhCPhdCPh)}Ru3(CO)6 (4a), which then transforms into
4 via the cleavage of a Ru(3)-C bond (from η4 to η3)
followed by the formation of a new Ru-C σ bond.
{μ3-η2:η3:η5-(C5H4N)(C9H5)(CPhCPhdCPhCPh)}Ru3(CO)6
(4), and {μ2-η1:η5-(C5H4N)(C9H5)(PhCdCPh)}Ru3(CO)4
(μ3-η2-PhCdCPh)2 (5) in 66%, 7%, and 12% yields, respec-
tively (Scheme 1). The 1H NMR spectrum of 3 shows eight
groups of peaks at 8.89-6.05 ppm for the pyridyl and benzo
protons and one singlet at 5.13 ppm for the C5 ring proton of
indenyl. Its IR spectrum only shows two terminal carbonyl
absorptions at 1965 and 1922 cm-1. Single-crystal X-ray
diffraction analysis revealed that complex 3 is a dinuclear
complex incorporating three diphenylacetylene molecules:
one is inserted into the Ru-C(η1) bond, and the others are
(8) For recent examples, see: (a) Ovchinnikov, M. V.; Klein, D. P.;
Guzei, I. A.; Choi, M.-G.; Angelici, R. J. Organometallics 2002, 21, 617.
(b) Chen, M.-C.; Eichbert, M. J.; Vollhardt, K. P. C.; Sercheli, R.;
Wasser, I. M.; Whitener, G. D. Organometallics 2002, 21, 749. (c)
Yamamoto, Y.; Miyabe, Y.; Itoh, K. Eur. J. Inorg. Chem. 2004, 3651.
(d) Yamazaki, S.; Taira, Z.; Yonemura, T.; Deeming, A. J. Organome-
tallics 2006, 25, 849. (e) Shima, T.; Ichikawa, T.; Suzuki, H. Organome-
tallics 2007, 26, 6329.
Complex 5 is a triruthenium complex incorporating three
diphenylacetylene molecules. Its 1H NMR spectrum shows a
doublet at 5.41 ppm for two phenyl protons, which is much

Article
Organometallics, Vol. 30, No. 4, 2011 679
Figure 5. ORTEP diagram of 6. Thermal ellipsoids are shown
at the 50% probability level. Hydrogen atoms have been
omitted for clarity, except for H(29). Selected bond lengths
(A):Ru(1)-N(1) = 2.1715(19), Ru(1)-C(28) = 2.227(2), Ru(1)-
C(29) = 2.228(2), Ru(1)-Ru(3) = 2.6449(3), Ru(1)-Ru(2) =
2.9211(5), Ru(2)-Ru(3) = 2.8868(4), Ru(3)-C(28) = 2.090(2),
C(28)-C(29) = 1.409(3).
Figure 4. ORTEP diagram of 5. Thermal ellipsoids are shown
at the 30% probability level. Hydrogen atoms have been
omitted for clarity. Selected bond lengths: Ru(1)-C(47) =
2.066(5), Ru(1)-C(26) = 2.098(6), Ru(1)-N(1) = 2.134(5),
Ru(1)-C(40) = 2.141(6), Ru(1)-Ru(2) = 2.6298(8), Ru(1)-
Ru(3) = 2.8709(10), Ru(2)-C(40) = 2.139(6), Ru(2)-C(54) =
2.146(5), Ru(2)-C(33) = 2.169(6), Ru(2)-C(47) = 2.183(6),
Ru(2)-Ru(3) = 2.6938(8), Ru(3)-C(54) = 2.103(6), Ru(3)-
C(33) = 2.122(5), C(19)-C(26) = 1.338(7), C(33)-C(40) =
1.412(8), C(47)-C(54) = 1.400(8).
Scheme 4
Scheme 3
farther upfield than the other signals, due to the deshielding
effect of surrounding groups. From its molecular structure
(Figure 4) it is found that one alkyne is inserted into the
Ru-C(η1) bond; the other two coordinate with the Ru3 core,
both in a μ3-η2 mode. The C(33)dC(40) and C(47)dC(54)
bonds are parallel to the Ru(1)-Ru(3) bond. This type of
bonding mode has been observed in a number of clusters.9
The bridging PhC(19)dC(26)Ph ligand does not coordinate
with any Ru atom; therefore, the C(19)dC(26) distance
(1.338(7) A) is much shorter than the C(33)dC(40) and
C(47)dC(54) distances (1.412(8), 1.400(8) A).TheRu(1)-Ru(2)
and Ru(2)-Ru(3) distances (2.6298(8), 2.6938(8) A) are com-
parable to the corresponding Ru-Ru distances in the complex
(μ3-η2-PhCdCPh)2Ru3(CO)8 (2.6566(6), 2.6646(7) A),9b but
the Ru(1)-Ru(3) distance (2.8709(10) A) is much longer
than the corresponding Ru-Ru distance (2.7264(7) A).
Complexes 3-5 could also be obtained by a one-pot reac-
tion of 1 with excess diphenylacetylene, and the total yield
(61%) is slightly higher than that for two steps (54%)
(Scheme 1).
Reaction of 1 with Phenylacetylene. Thermal treatment of 1
with 1 equiv of phenylacetylene gave the trinuclear complex
{μ3-η1:η2:η5-(C5H4N)(C9H5)(HCdCPh)}Ru3(CO)7 (6; 24%),
in addition to recovered 1 (25%) (Scheme 4).
(9) (a) Rivomanana, S.; Lavigne, G.; Lugan, N.; Bonnet, J.-J.; Yanez,
R.; Mathieu, R. J. Am. Chem. Soc. 1989, 111, 8959. (b) Rivomanana, S.;
Lavigne, G.; Lugan, N.; Bonnet, J.-J. Organometallics 1991, 10, 2285. (c)
Takao, T.; Takemori, T.; Moriya, M.; Suzuki, H. Organometallics 2002,
21, 5190. (d) Srinivasan, P.; Leong, W. K. Eur. J. Inorg. Chem. 2006, 464.
The 1H NMR spectrum of 6 shows five groups of peaks at
8.72-7.14 ppm for the pyridyl and benzo protons, one
singlet at 6.73 ppm for the proton of the bridging CHdCPh

680 Organometallics, Vol. 30, No. 4, 2011
Chen et al.
Figure 6. ORTEP diagram of 7. Thermal ellipsoids are shown
at the 30% probability level. Hydrogen atoms have been
omitted for clarity, except for H(1) and H(29). Selected bond
lengths (A): Ru(1)-Ru(2) = 2.7878(4), Ru(2)-C(21) = 2.276(3),
Ru(2)-C(22) = 2.346(3), Ru(2)-C(29) = 2.300(4), Ru(2)-
C(30) = 2.326(3), Ru(2)-Ru(3) = 2.7752(5), Ru(3)-C(21) =
2.106(3), Ru(3)-C(30) = 2.077(4), Ru(3)-N(1) = 2.204(3),
C(21)-C(22) = 1.421(5), C(22)-C(29) = 1.458(5), C(29)-
C(30) = 1.415(5).
Figure 7. ORTEP diagram of 8. Thermal ellipsoids are shown
at the 30% probability level. Hydrogen atoms have been
omitted for clarity, except for H(28). Selected bond lengths
(A): Ru(1)-C(20) =2.265(5), Ru(1)-C(21) = 2.295(5), Ru(1)-
C(28) = 2.267(5), Ru(1)-C(29) = 2.285(5), Ru(1)-Ru(2) =
2.6955(9), Ru(2)-C(20) = 2.113(5), Ru(2)-C(29) = 2.041(5),
Ru(2)-N(1) = 2.184(4), C(20)-C(21) = 1.431(6), C(21)-C(28)
= 1.427(6), C(28)-C(29) = 1.412(6).
CCPhCHCPh ligand, and a doublet of doublets at 3.29 ppm
for the C5 ring proton of indenyl. The doublet of doublets for
the C5 ring proton of indenyl indicates that the indenyl group
does not coordinate with the Ru atom in an η5 mode. Its
IR spectrum shows four terminal and one bridging carbonyl
ligand, and one singlet at 4.89 ppm for the C5 ring proton of
indenyl. The structure of 6 is similar to that of 2 (Figure 5).
The Ru(1)-Ru(3) and Ru(2)-Ru(3) distances (2.6449(3),
2.8868(4) A) are comparable to the corresponding Ru-Ru
distances in 2 (2.6466(6), 2.8946(6) A). The Ru(1)-Ru(2)
distance (2.9211(5) A) is slightly longer than the correspond-
ing Ru-Ru distance in 2 (2.8939(6) A). The CHdCPh ligand
coordinates with Ru(1) in an η2 mode and with Ru(3) in an η1
mode.
absorption at 2031, 2000, 1969, 1945, and 1882 cm-1 8d
.
Single-crystal X-ray diffraction analysis showed that
complex 8 is a dinuclear ruthenacyclopentadiene complex
(Figure 7). The Ru(1)-Ru(2) distance (2.6955(9) A) is
slightly longer than the Ru-Ru distance in complex 3
(2.6649(4) A). The Ru(1) and Ru(2) atoms are bridged by a
μ2-η2:η4-CdCPhCHdCPh fragment and a μ2-CO group.
The C(20)-C(21), C(21)-C(28), and C(28)-C(29) bond
lengths are 1.431(6), 1.427(6), and 1.412(6) A, respectively.
The dihedral angle between the C(20)-C(21)-C(28)-C(29)
and C(20)-Ru(2)-C(29) planes is 7.4°.
On thermal treatment of complex 7 in refluxing toluene for
20 h, complex 8 was obtained in 12% yield, in addition to
recovered 7 (60%) (Scheme 4). Similar to the case for
complexes 3-5, complexes 7 and 8 could also be obtained
by the one-pot reaction of 1 with excess phenylacetylene. The
total yield (54%) is much higher than that for two steps
(14%) (Scheme 4).
A possible formation mechanism of complexes 7 and 8 is
shown in Scheme 5. First, complex 6 transforms to 6a, and
then phenylacetylene inserts into the Ru-C(Ph) bond to
form 7a, followed by the oxidative addition of a C-H bond
to the Ru atom to form a five-membered ring, accompanied
by the cleavage of a Ru-Ru bond to form complex 7. Then
the μ2-H atom transfers to the indenyl ring to form complex
8,10 accompanied by the cleavage of the η5-indenyl-Ru
bond and a Ru-Ru bond.
Reaction of 6 with Phenylacetylene. Similar to the case for
complex 2, complex 6 could further react with excess pheny-
lacetylene to give the trinuclear and dinuclear complexes {μ3-
η2:η4:η5-(C5H4N)(C9H5)(CdCPhCHdCPh)}(μ2-H)Ru3-
(CO)6 (7) and {μ2-η2:η4-(C5H4N)(C9H6)(CdCPhCHdCPh)}
Ru2(CO)4(μ2-CO) (8) in 37% and 22% yields, respectively
(Scheme 4). The 1H NMR spectrum of complex 7 shows six
groups of peaks at 9.16-7.06 ppm for the pyridyl and benzo
protons, one singlet at 7.01 ppm for the proton of the
bridging CCPhCHCPh ligand, one singlet at 4.08 ppm for
the C5 ring proton of indenyl, and one singlet at -13.11 ppm
for Ru-H, indicating that its structure is different from
those of complexes 3-5. Single-crystal X-ray diffraction
analysis showed that complex 7 is a trinuclear ruthenacyclo-
pentadiene complex (Figure 6).8 The Ru(2)-Ru(3) distance
(2.7752(5) A) is longer than the Ru-Ru distance in 3
(2.6649(4) A). The Ru(1)-Ru(2) distance is 2.7878(4) A.
The long distance (4.058 A) between Ru(1) and Ru(3) atoms
indicates that they do not bond to each other. The Ru(2) and
Ru(3) atoms are bridged by a (μ2-η2:η4-CdCPhCHdCPh)
fragment and a μ2-H atom. The C(21)-C(22), C(22)-C(29),
and C(29)-C(30) bond lengths are 1.421(5), 1.458(5), and
1.415(5) A, respectively. The dihedral angle between the
C(21)-C(22)-C(29)-C(30) and C(21)-Ru(3)-C(30) planes
is 11.5°.
Catalytic Reactions of 3-(2-Pyridyl)indene with Alkynes.
Alkynes could react with 3-(2-pyridyl)indene to give C-H/
alkyne coupling products (9-11) when using Ru3(CO)12
The 1H NMR spectrum of complex 8 shows four groups of
peaks at 9.54-7.01 ppm for the pyridyl and benzo protons,
one singlet at 6.54 ppm for the proton of the bridging
(10) Stradiotto, M.; McGlinchey, M. J. Coord. Chem. Rev. 2001,
219-221, 311.

Article
Organometallics, Vol. 30, No. 4, 2011 681
Scheme 5
Table 1. Ru3(CO)12-Catalyzed C-H/Alkyne Couplinga
diphenylacetylene and phenylacetylene were studied. For
phenylacetylene, after the insertion of two molecules of
phenylacetylene into the Ru-C bond, the oxidative addition
of a C-H bond to the Ru atom can further occur to form a
five-membered ring. This difference may be parts of the
reason the reactivities of terminal and internal alkynes were
quite different in the Ru3(CO)12-catalyzed C-H/alkyne cou-
pling reactions.
entry catalyst
alkyne
product
yieldb (%)
1
2
3
4
5
6
Ru3(CO)12 R = R0 = Ph
R = R0 = Ph (9)
67
38
43
N/A
N/A
20
Ru3(CO)12 R = Ph, R0 = Me R = Ph, R0 = Me (10)
Experimental Section
Ru3(CO)12 R = R0 = Et
R = R0 = Et (11)
Ru3(CO)12 R = R0 = CO2Me N/Ac
Ru3(CO)12 R = Ph, R0 = H N/Ad
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 and VARIAN AS-400 spectro-
meters, while IR spectra were recorded as KBr disks on a Nicolet
380 FT-IR spectrometer. Elemental analyses were performed on
a Perkin-Elmer 240C analyzer. [μ2-η5:η1-(C5H4N)(C9H5)]Ru3-
(CO)9 (1) was synthesized according to the literature procedure.8
Reaction of 1 with Diphenylacetylene. Method A. A solution
of 0.20 g (0.27 mmol) of 1 and 0.048 g (0.27 mmol) of dipheny-
lacetylene in 30 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
developed a yellow band, which gave 0.15 g (64%) of 2 as orange
crystals. Mp: 145 °C dec. Anal. Calcd for C35H19NO7Ru3:
C, 48.39; H, 2.20; N, 1.61. Found: C, 48.60; H, 2.55; N, 1.66.
1H NMR (CDCl3): δ 8.52 (d, J = 5.2 Hz, 1H, Py H), 7.62 (t, J =
7.4 Hz, 1H, Py H), 7.55-7.48 (m, 2H, Py H), 7.43-7.31 (m, 3H,
1
R = R0 = Ph
R = R0 = Ph (9)
a Reaction conditions: 3-(2-pyridyl)indene (1 mmol), acetylene
(5 mmol), catalyst (0.02 mmol), toluene 5 mL, under reflux for 20 h.
b Isolated yield. c The main product is hexacarbomethoxybenzene, de-
termined by GC-mass. d Unidentified product.
(2%) as catalyst (Table 1), but the reaction with phenylace-
tylene did not work under the same conditions (entry 5).
Complexes 9-11 only exist as E isomers, according to their
1H NMR spectra. For entry 2, the formation of two regioi-
somers is possible, but the C-C bond formation took place
in a regiospecific manner. When dimethyl acetylenedicar-
boxylate was used, only hexacarbomethoxybenzene was
formed via trimerization (entry 4). When 1 was used instead
of Ru3(CO)12, the reaction could also proceed, but with low
yield (entry 6).
Why did phenylacetylene fail to couple with 3-(2-pyri-
dyl)indene in presence of Ru3(CO)12? For the rhodium
catalyst system the failure in C-H/alkyne coupling of term-
inal alkynes was attributed to the oligomerization of terminal
alkynes.5 In our system, according to the reaction results of
phenylacetylene with complex 1, we suppose that two mole-
cules of phenylacetylene could insert into the Ru-C bond of
the intermediate 12 to form 13, followed by oxidative addi-
tion of the C-H bond of the PhCdCH fragment and
elimination of a hydrogen to form 14 (Scheme 6). The
formation of this kind of compound may kill the catalyst.
In conclusion, reactions of the trinuclear ruthenium car-
bonyl complex {μ2-η5:η1-(C5H4N)(C9H5)}Ru3(CO)9 (1) with
Ar H), 7.22-6.70 (m, 11H, Ar H), 5.01 (s, 1H, Cp H). IR (νCO
,
cm-1): 2053 (s), 2006 (m), 1988 (s), 1981 (s), 1953 (m), 1942 (m),
1913 (m).
Method B. Using a procedure similar to that described above,
reaction of 1 (0.20 g, 0.27 mmol) with diphenylacetylene (0.24 g,
1.3 mmol) in 30 mL of toluene under reflux for 20 h gave 0.13 g
(48%) of 3 as orange crystals, 0.013 g (5%) of 4 as dark crystals,
and 0.025 g (8%) of 5 as red crystals. The following are data for
3. Mp: 190 °C dec. Anal. Calcd for C58H39NO2Ru2: C, 70.79; H,
1
3.99; N, 1.42. Found: C, 70.48; H, 3.60; N, 1.52. H NMR-
(CDCl3): δ 8.89 (d, J = 5.5 Hz, 1H, Py H), 7.68-7.61 (m, 3H,
Py H), 7.56 (d, J = 8.6 Hz, 1H, Ar H), 7.36 (d, J = 7.5 Hz, 1H,
Ar H), 7.29 (t, J = 7.2 Hz, 2H, Ar H), 7.09-6.65 (m, 25H, Ar H),
6.50-6.45 (m, 2H, Ar H), 6.22 (d, J = 8.6 Hz, 1H, Ar H),

682 Organometallics, Vol. 30, No. 4, 2011
Chen et al.
Scheme 6
Table 2. Crystal Data and Summary of X-ray Data Collection
2 0.5CH2Cl2
3 CH2Cl2
4 CH2Cl2 0.75H2O
5 CH2Cl2
6
7
8
3
3
3
3
3
formula
C
35.50H20-
ClNO7Ru3
C59H41Cl2-
NO2Ru2
1068.97
113(2)
C49H32.5Cl2-
NO6.75Ru3
1117.37
294(2)
0.71073
monoclinic
P21/c
16.572(14)
10.185(9)
27.55(2)
90
98.248(15)
90
C61H41Cl2-
NO4Ru3
1226.06
294(2)
0.71073
monoclinic
P21/c
20.532(5)
13.568(3)
18.234(4)
90
102.230(4)
90
C29H15
NO7Ru3
792.63
-
C36H21
NO6Ru3
866.75
-
C35H21
NO5Ru2
737.67
-
fw
T, K
λ, A
cryst syst
space group
a, A
b, A
c, A
911.19
113(2)
0.71070
orthorhombic triclinic
Pbca
11.884(2)
17.465(3)
30.543(6)
90
90
90
6339(2)
8
1.909
1.548
3560
0.20 ꢀ 0.20
ꢀ 0.20
2.17-27.89
55 570
113(2)
294(2)
294(2)
0.71070
0.71070
monoclinic
P21/c
9.7376(15)
15.292(2)
17.301(3)
90
91.758(2)
90
2574.9(7)
4
2.045
1.788
1536
0.20 ꢀ 0.18
ꢀ 0.14
2.09-27.87
31 814
0.71073
monoclinic
P21/n
10.0956(11)
15.8247(18)
19.840(2)
90
92.212(2)
90
3167.3(6)
4
1.818
1.460
1696
0.20 ꢀ 0.18
ꢀ 0.12
1.65-26.44
17 802
0.71073
monoclinic
P21/n
10.591(3)
17.577(5)
16.021(4)
90
97.542(5)
90
2956.8(14)
4
1.657
1.066
1464
0.28 ꢀ 0.14
ꢀ 0.14
1.73-25.02
12 588
P1
11.7745(17)
12.896(2)
15.508(2)
100.362(3)
91.551(3)
90.523(3)
2315.3(6)
2
R, deg
β, deg
γ, deg
V, A3
4602(7)
4
1.613
1.138
2214
4964(2)
4
1.640
1.060
2448
Z
Dcalcd, g cm-3
μ, mm-1
F(000)
cryst size, mm
1.533
0.814
1080
0.16 ꢀ 0.14
0.24 ꢀ 0.20
0.18 ꢀ 0.16
ꢀ 0.10
ꢀ 0.16
ꢀ 0.12
θ range, deg
no. of rflns collected
1.73-27.86
29 194
1.24-25.02
23 119
1.01-26.43
27 950
no. of indep rflns/Rint 7563/0.0652
10 951/0.0308
614
1.034
8108/0.0423
622
1.154
0.0506/0.1200
0.0767/0.1338
0.986, -1.270
10 145/0.0769 6143/0.0427
362
1.038
0.0469/0.0949 0.0244, 0.0536 0.0297, 0.0685 0.0402, 0.0717
0.1172/0.1221 0.0304, 0.0562 0.0481, 0.0782 0.0845, 0.0847
6487/0.0306
419
1.049
5165/0.0657
388
1.024
no. of params
470
1.204
650
0.988
goodness of fit on F2
R1, wR2 (I > 2σ(I))
R1, wR2 (all data)
largest diff peak,
0.0466/0.0852 0.0350/0.0795
0.0507/0.0868 0.0405/0.0829
0.763, -0.725 0.608, -0.750
0.723, -0.676 0.429, -0.682
1.057, -0.699
0.689, -0.742
hole (e A-3
)
6.05 (d, J = 7.0 Hz, 2H, Ar H), 5.13 (s, 1H, Cp H). IR (νCO
,
Ar H), 6.73 (s, 1H, dCH), 4.89 (s, 1H, Cp H). IR (νCO, cm-1):
2053 (s), 2002 (s), 1992 (s), 1970 (s), 1947 (m), 1916 (s).
cm-1): 1965 (s), 1922 (s). The following are data for 4. Mp:
130-131 °C. Anal. Calcd for C48H29NO6Ru3: C, 56.58; H, 2.87;
N, 1.37. Found: C, 56.20; H, 3.01; N, 1.21. 1H NMR (CDCl3): δ
8.24 (d, J = 8.6 Hz, 1H, Py H), 7.92 (d, J = 5.4 Hz, 1H, Ar H),
7.75-7.64 (m, 3H, Py H), 7.54 (d, J = 8.0 Hz, 1H, Ar H),
7.46-6.68 (m, 22H, Ar H), 5.27 (s, 1H, Cp H). IR (νCO, cm-1):
2028 (s), 1995 (s), 1969 (s), 1925 (m), 1919 (m), 1911 (m). The
following are data for 5. Mp: 130-131 °C. Anal. Calcd for
C60H39NO4Ru3: C, 63.15; H, 3.44; N, 1.23. Found: C, 63.00; H,
3.80; N, 1.28. 1H NMR(CDCl3): δ 8.03(d, J = 8.6 Hz, 1H, Py H)
(7.71 (m, 2H), 7.58 (m, 2H), 7.50-6.53 (m, 29H)) (Py H and Ar
H), 6.19 (d, J = 7.4 Hz, 2H, Ar H), 5.68 (s, 1H, Cp H), 5.41 (d, J
= 7.4 Hz, 2H, Ar H). IR (νCO, cm-1): 2005 (s), 1976 (s), 1933 (s).
Reaction of 2 with Diphenylacetylene. Using a procedure
similar to that described above, reaction of 2 (0.10 g, 0.12 mmol)
with diphenylacetylene (0.082 g, 0.46 mmol) in 30 mL of reflux-
ing toluene for 20 h gave 3 (0.075 g, 66%), 4 (0.008 g, 7%), and 5
(0.016 g, 12%).
Method B. Using a procedure similar to that described above,
reaction of 1 (0.20 g, 0.27 mmol) with phenylacetylene (0.14 g,
1.4 mmol) in 30 mL of refluxing toluene for 20 h gave 7 (0.090 g,
39%) and 8 (0.030 g, 15%), both as orange crystals. The fol-
lowing are data for 7. Mp: 150 °C dec. Anal. Calcd for
C36H21NO6Ru3: C, 49.88; H, 2.44; N, 1.62. Found: C, 49.53;
H, 2.80; N, 1.63. 1H NMR (CDCl3): δ 9.16 (d, J = 5.3 Hz, 1H,
Py H) (8.00 (d, J = 7.8 Hz, 1H), 7.93-7.75 (m, 4H), 7.46 (m,
3H), 7.35-7.11 (m, 8H)) (Py H and Ar H), 7.06 (d, J = 7.7 Hz,
1H, Ar H), 7.01 (s, 1H, PhCdCH), 4.08 (s, 1H, Cp H), -13.11 (s,
1H, Ru-H). IR (νCO, cm-1): 2025 (s), 2004 (s), 1973 (s), 1954 (s),
1926 (s). The following are data for 8. Mp: 180 °C dec. Anal.
Calcd for C35H21NO5Ru2: C, 56.99; H, 2.87; N, 1.90. Found: C,
56.65; H, 3.01; N, 1.98. 1H NMR (CDCl3): δ 9.54 (d, J = 5.6 Hz,
1H, Py H), 7.94 (d, J = 7.7 Hz, 1H, Py H), 7.87 (t, J = 6.9 Hz,
2H, Py H), 7.60-7.01 (m, 14H, Ar H), 6.54 (s, 1H, PhCdCH),
3.29 (dd, J = 23.4, 9.7 Hz, 2H, Cp H). IR (νCO, cm-1): 2031 (s),
2000 (s), 1969 (s), 1945 (s), 1882 (s).
Reaction of 6 with Phenylacetylene. Using a procedure similar
to that described above, reaction of 6 (0.050 g, 0.063 mmol) with
phenylacetylene (0.026 g, 0.25 mmol) in 30 mL of refluxing
toluene for 20 h gave 7 (0.020 g, 37%) and 8 (0.010 g, 22%).
Thermal Reaction of 7. Using a procedure similar to that
described above, thermal treatment of 7 (0.050 g, 0.058 mmol) in
30 mL of refluxing toluene for 20 h gave 8 (0.005 g, 12%), in
addition to unreacted 7 (0.030 g, 60%).
Reaction of 1 with Phenylacetylene. Method A. Using a
procedure similar to that described above, reaction of 1 (0.20
g, 0.27 mmol) with phenylacetylene (0.027 g, 0.27 mmol) in 30
mL of refluxing toluene for 20 h gave 6 (0.050 g, 24%) as orange
crystals, in addition to unreacted 1 (0.050 g, 25%). Mp: 175 °C
dec. Anal. Calcd for C29H15NO7Ru3: C, 43.94; H, 1.91; N, 1.77.
Found: C, 43.94; H, 2.31; N, 1.82. 1H NMR (CDCl3): δ 8.72 (d,
J = 5.4 Hz, 1H, Py H), 7.89 (t, J = 7.8 Hz, 1H, Py H), 7.59 (d,
J = 7.8 Hz, 1H, Py H), 7.53 (m, 1H, Py H), 7.42-7.14 (m, 11H,

Article
Catalytic Reaction of 3-(2-Pyridyl)indene with Alkynes. A
Organometallics, Vol. 30, No. 4, 2011 683
13C NMR (CDCl3): δ 149.2, 144.7, 142.6, 136.5, 129.8, 126.4,
124.6, 124.0, 123.3, 121.6, 121.3, 42.3, 30.8, 22.6, 13.8, 13.2. MS
(ESI): m/z 276([Mþ]).
Catalytic Reaction of 3-(2-Pyridyl)indene with Phenylacetylene.
Using a procedure similar to that described above, on thermal
treatment of 0.19 g (1.0 mmol) of 3-(2-pyridyl)indene, 0.51 g (5.0
mmol) of phenylacetylene, and 0.013 g (0.02 mmol) of Ru3(CO)12
in 5 mL of refluxing toluene for 24 h, only unreacted 3-(2-
pyridyl)indene (0.15 g, 78%) was recovered.
Crystallographic Studies. Single crystals of complexes 2-8
suitable for X-ray diffraction were obtained from hexane/
CH2Cl2 solution. Data collection was performed on a Bruker
Smart 1000 (for 4, 5, 7, and 8) or a Rigaku MM-OO7/Saturn
70 (for 2, 3, and 6) diffractometer, using graphite-monochro-
mated Mo KR radiation (ω-2θ scans). Semiempirical absorp-
tion corrections were applied for all complexes. The structures
were solved by direct methods and refined by full-matrix least
squares. All calculations were carried out with the SHELXL-97
program system. The crystal data and summary of X-ray data
collection are given in Table 2.
solution of 1.0 mmol of 3-(2-pyridyl)indene, 5.0 mmol of an
alkyne, and 0.013 g (0.02 mmol) of Ru3(CO)12 in 5 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 developed the product.
Complex 9: pale yellow solid, yield 0.25 g (67%). Mp: 53-54
°C. Anal. Calcd for C28H21N: C, 90.53; H, 5.70; N, 3.77. Found:
C, 90.23; H, 6.08; N, 3.50. 1H NMR (CDCl3): δ 8.53 (d, J = 4.8
Hz, 1H, Py H), 7.85 (t, J = 7.6 Hz, 1H, Py H), 7.50-7.00 (m,
16H, Py H and Ar H), 6.97 (s, 1H, dCH), 3.69 (s, 2H, Cp H). 13
C
NMR (CDCl3): δ 149.2, 143.4, 141.8, 137.9, 137.5, 135.9, 130.3,
128.8, 128.6, 127.8, 127.4, 127.1, 126.8, 125.4, 123.9, 123.8,
122.3, 121.9, 41.9. MS (ESI): m/z 371 ([Mþ]).
Complex 10: pale yellow solid, yield 0.116 g (38%). Mp 48-
50 °C. Anal. Calcd for C23H19N: C, 89.28; H, 6.19; N, 4.53. Found:
C, 89.43; H, 6.21; N, 4.54. 1H NMR(CDCl3): δ 8.76 (d,
J = 4.4 Hz, 1H, Py H), 7.88 (d, J = 7.6 Hz, 1H, Py H), 7.74 (d,
J = 8.7 Hz, 1H, Py H), 7.65-7.16 (m, 10H, Py H and Ar H), 6.05
(m, 1H, dC-H), 3.58 (s, 2H, Cp H), 1.44 (d, J= 7.0 Hz, 3H, Me-H).
13C NMR (CDCl3): δ 143.1, 141.3, 137.2, 136.3, 129.4, 128.5, 127.6,
127.1, 126.6, 126.5, 125.8, 125.0, 123.6, 123.4, 121.8, 121.7, 120.0, 118.2,
42.0, 15.6. MS (ESI) m/z: 310([Mþ]).
Complex 11: pale yellow oil, yield 0.118 g (43%). Anal. Calcd
for C20H21N: C, 87.23; H, 7.69; N, 5.09. Found: C, 87.52; H,
7.61; N, 5.13. 1H NMR (CDCl3): δ 8.75 (d, J = 4.4 Hz, 1H, Py
H), 7.75 (d, J = 7.6 Hz, 1H, Py H), 7.66 (t, J = 7.6 Hz, 1H, Py
H), 7.46 (d, J = 7.6 Hz, 2H, Ar H), 7.30 (t, J = 7.6 Hz, 1H, Py
H), 7.20 (t, J = 7.2 Hz, 2H, Ar H), 5.30 (t, J = 7.3 Hz, 1H, d
CH), 3.60 (s, 2H, Cp H), 2.26 (m, 2H, Et H) = 1.71 (m, 2H, Et
H), 1.05 (t, J = 7.5 Hz, 3H, Et H), 0.65 (t, J = 7.5 Hz, 3H, Et H).
Acknowledgment. We are grateful to 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: CIF files giving crystal-
lographic details for 2-8. This material is available free of
charge via the Internet at http://pubs.acs.org.