Self-assembled chloro-bridged (arene)ruthenium metallo-prisms: Synthesis and molecular structure of cationic complexes of the type [Ru 6(η6-arene)6(μ3-tpt-κN) 2(μ-Cl)6]6+ (tpt = 2,4,6-tris(pyridinyl)-1, 3,5-triazine)

Article abstract of DOI:10.1021/om060843k

Cationic (arene)ruthenium-based hexanuclear complexes with trigonal-prismatic structures have been synthesized in good yield by self-assembly of only two components: the dinuclear (arene)ruthenium complexes [Ru(η⁶-arene)(μ-Cl)Cl]₂ (arene = p-Pr ⁱC₆H₄Me, C₆Me₆) react in water with 2,4,6-tris(pyridinyl)-1,3,5-triazine (tpt) derivatives in the presence of AgO₃SCF₃ to form hexanuclear cations of the general formula [Ru₆(η⁶-arene) ₆(μ₃-tpt-κN)₂(μ-Cl) ₆]⁶⁺. In the presence of 2,4,6-tris(pyridin-4-yl)-1,3,5- triazine (4-tpt) the prismatic cations [Ru₆-p-PrⁱC ₆H₄Me)₆(μ₃-4-tpt-κN) ₂(μ-Cl)₆]⁶⁺^ (3) and [Ru₆(η ⁶-C₆Me₆)₆(μ₃-4-tpt-/ cκN)₂(μ-Cl)₆]⁶⁺ (4) have been isolated as the triflate salts, whereas with 2,4,6-tris(pyridin-3-yl)-1,3,5-triazine (3-tpt) [Ru₆(η⁶-p-PrⁱC₆H ₄Me)₆(μ₃3-tpt-κN)₂(μ-Cl) ₆]⁶⁺ (7) and [Ru₆(η⁶-C ₆Me₆)₆(μ₃-3-tpt-κN) ₂(μ-Cl)₆]⁶⁺ (8) have been obtained and isolated as the triflate salts. In all cases, the neutral intermediates initially formed prior to the addition of silver triflate have been isolated and characterized as well: [Ru₃(η⁶-p-PrⁱC ₆H₄Me)₃(μ₃-4-tpt-κN)Cl ₆] (1), [Ru₃(η⁶-C₆Me ₆)₃(μ₃-4-tpt-κN)Cl₆] (2), [Ru₃(η⁶-p-PrⁱC₆H ₄Me)₃-(η₃-3-tpt-κN)Cl₆] (5), and [Ru₃(η⁶-C₆Me₆) ₃(μ₃-3-tpt-κN)Cl₆] (6), respectively. In the case of a trigonal-prismatic hexacation containing p-cymene and 3-tpt ligands, the NMR spectra reveal a mixture of the two isomers 7a and 7b, the formation of which can be rationalized by molecular modeling. The single-crystal structure analyses of [Ru₆(η₆-p-PrⁱC ₆H₄Me)₆(μ₃-4-tpt-κN) ₂(μ-Cl)₆][O₃SCF₃]₆ ([3][O₃SCF₃]₆), [Ru₆(η ⁶-C₆Me₆)₆(μ₃-4-tpt- κN)₂(μ-Cl)₆][O₃SCF₃] ₆ ([4][O₃SCF₃]₆), and [Ru ₆(η⁶-C₆Me₆)₆(μ ₃-3-tpt-κN)₂(μ-Cl)₆][O ₃-SCF₃]₆ ([8][O₃SCF ₃]₆) reveal strong π stacking interactions between the two tpt subunits of the trigonal prisms.

Full text of DOI:10.1021/om060843k

Organometallics 2007, 26, 915-924
915
Self-Assembled Chloro-Bridged (Arene)ruthenium Metallo-Prisms:
Synthesis and Molecular Structure of Cationic Complexes of the
Type [Ru6(η6-arene)6(µ3-tpt-KN)2(µ-Cl)6]6+ (tpt )
2,4,6-tris(pyridinyl)-1,3,5-triazine)
Padavattan Govindaswamy, Georg Su¨ss-Fink, and Bruno Therrien*
Institut de Chimie, UniVersite´ de Neuchaˆtel, Case postale 158, CH-2009 Neuchaˆtel, Switzerland
ReceiVed September 14, 2006
Cationic (arene)ruthenium-based hexanuclear complexes with trigonal-prismatic structures have been
synthesized in good yield by self-assembly of only two components: the dinuclear (arene)ruthenium
complexes [Ru(η6-arene)(µ-Cl)Cl]2 (arene ) p-PriC6H4Me, C6Me6) react in water with 2,4,6-tris(pyridinyl)-
1,3,5-triazine (tpt) derivatives in the presence of AgO3SCF3 to form hexanuclear cations of the general
formula [Ru6(η6-arene)6(µ3-tpt-κN)2(µ-Cl)6]6+. In the presence of 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine
(4-tpt) the prismatic cations [Ru6(η6-p-PriC6H4Me)6(µ3-4-tpt-κN)2(µ-Cl)6]6+ (3) and [Ru6(η6-C6Me6)6(µ3-
4-tpt-κN)2(µ-Cl)6]6+ (4) have been isolated as the triflate salts, whereas with 2,4,6-tris(pyridin-3-yl)-
1,3,5-triazine (3-tpt) [Ru6(η6-p-PriC6H4Me)6(µ3-3-tpt-κN)2(µ-Cl)6]6+ (7) and [Ru6(η6-C6Me6)6(µ3-3-tpt-
κN)2(µ-Cl)6]6+ (8) have been obtained and isolated as the triflate salts. In all cases, the neutral intermediates
initially formed prior to the addition of silver triflate have been isolated and characterized as well: [Ru3-
(η6-p-PriC6H4Me)3(µ3-4-tpt-κN)Cl6] (1), [Ru3(η6-C6Me6)3(µ3-4-tpt-κN)Cl6] (2), [Ru3(η6-p-PriC6H4Me)3-
(µ3-3-tpt-κN)Cl6] (5), and [Ru3(η6-C6Me6)3(µ3-3-tpt-κN)Cl6] (6), respectively. In the case of a trigonal-
prismatic hexacation containing p-cymene and 3-tpt ligands, the NMR spectra reveal a mixture of the
two isomers 7a and 7b, the formation of which can be rationalized by molecular modeling. The single-
crystal structure analyses of [Ru6(η6-p-PriC6H4Me)6(µ3-4-tpt-κN)2(µ-Cl)6][O3SCF3]6 ([3][O3SCF3]6), [Ru6(η6-
C6Me6)6(µ3-4-tpt-κN)2(µ-Cl)6][O3SCF3]6 ([4][O3SCF3]6), and [Ru6(η6-C6Me6)6(µ3-3-tpt-κN)2(µ-Cl)6][O3-
SCF3]6 ([8][O3SCF3]6) reveal strong π stacking interactions between the two tpt subunits of the trigonal
prisms.
center possesses six coordination sites. Cotton and co-workers
have built up two- and three-dimensional architectures from
metal-metal paddlewheel units such as [Mo2(µ-DAniF-κN,N′)3-
(CH3CN)2]+ (DAniF ) N,N′-di-p-anisylformamidinate).6 Simi-
larly, the fac-Re(CO)3 corner system was judiciously chosen to
prepare molecular rectangles7 or triangular prisms.8 The triden-
Introduction
Self-assembly of supramolecular architectures with transition-
metal complexes is mainly dominated by square-planar metal
coordination geometries. Pioneered by Fujita in 19901 and
exploited by other groups,2 the combination of 90° coordination
building blocks and linear ligands to form square and rectangular
networks has been extensively studied. A few years later, the
same approach was used to generate three-dimensional net-
works.3 So far, a multitude of two- and three-dimensional
structures incorporating transition metals with square-planar
geometry have been synthesized.4 In the search for new building
blocks for the synthesis of supramolecular materials with
interesting properties, there is an increasing interest in using
transition-metal complexes with octahedral geometry.5 However,
it is essential to control the directional bonding, since the metal
(4) (a) Pirondini, L.; Bertolini, F.; Cantadori, B.; Ugozzoli, F.; Massera,
C.; Dalcanale, E. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 4911-4915 and
references therein. (b) Ovchinnikov, M. V.; Holliday, B. J.; Mirkin, C. A.;
Zakharov, L. N.; Rheingold, A. L. Proc. Natl. Acad. Sci. U.S.A. 2002, 99,
4927-4931 and references therein. (c) Kuehl, C. J.; Kryschenko, Y. K.;
Radhakrishnan, U.; Seidel, S. R.; Huang, S. D.; Stang, P. J. Proc. Natl.
Acad. Sci. U.S.A. 2002, 99, 4932-4936 and references therein. (d) Kuehl,
C. J.; Yamamoto, T.; Seidel, S. R.; Stang, P. J. Org. Lett. 2002, 4, 913-
915. (e) Kryschenko, Y. K.; Seidel, S. R.; Muddiman, D. C.; Nepomuceno,
A. I.; Stang, P. J. J. Am. Chem. Soc. 2003, 125, 9647-9652. (f) Crowley,
J. D.; Goshe, A. J.; Bosnich, B. Chem. Commun. 2003, 2824-2825. (g)
Fujita, M.; Tominaga, M.; Hori, A.; Therrien, B. Acc. Chem. Res. 2005,
38, 369-378 and references therein. (h) Caskey, D. C.; Michl, J. J. Org.
Chem. 2005, 70, 5442-5448. (i) Maurizot, V.; Yoshizawa, M.; Kawano,
M.; Fujita, M. Dalton Trans. 2006, 2750-2756.
(5) (a) Mukherjee, P. S.; Min, K. S.; Arif, A. M.; Stang, P. J. Inorg.
Chem. 2004, 43, 6345-6350. (b) Mahmoudkhani, A. H.; Coˆte´, A. P.;
Shimizu, G. K. H. Chem. Commun. 2004, 2678-2679.
(6) Cotton, F. A.; Lin, C.; Murillo, C. A. Acc. Chem. Res. 2001, 34,
759-771 and references therein.
(7) (a) Woessner, S. M.; Helms, J. B.; Shen, Y.; Sullivan, B. P. Inorg.
Chem. 1998, 37, 5406-5407. (b) Rajendran, T.; Manimaran, B.; Lee, F.-
Y.; Lee, G.-H.; Peng, S.-M.; Wang, C. M.; Lu, K.-L. Inorg. Chem. 2000,
39, 2016-2017. (c) Sun, S.-S.; Silva, A. S.; Brinn, I. M.; Lees, A. J. Inorg.
Chem. 2000, 39, 1344-1345. (d) Rajendran, T.; Manimaran, B.; Lee, F.-
Y.; Chen, P.-J.; Lin, S.-C.; Lee, G.-H.; Peng, S.-M.; Chen, Y.-J.; Lu, K.-L.
Dalton Trans. 2001, 3346-3351. (e) Sun, S.-S.; Lees, A. J. Inorg. Chem.
2001, 40, 3154-3160.
* To whom correspondence should be addressed. E-mail:
bruno.therrien@unine.ch.
(1) Fujita, M.; Yazaki, J.; Ogura, K. J. Am. Chem. Soc. 1990, 112, 5645-
5647.
(2) (a) Kuehl, C. J.; Huang, S. D.; Stang, P. J. J. Am. Chem. Soc., 2001,
123, 9634-9641. (b) Moriuchi, T.; Miyaishi, M.; Hirai, T. Angew. Chem.,
Int. Ed. 2001, 40, 3042-3045. (c) Das, N.; Mukherjee, P. S.; Arif, A. M.;
Stang, P. J. J. Am. Chem. Soc. 2003, 125, 13950-13951. (d) Mukherjee,
P. S.; Das, N.; Kryschenko, Y. K.; Arif, A. M.; Stang, P. J. J. Am. Chem.
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J. Org. Lett. 2004, 6, 2093-2096. (f) Yoshizawa, M.; Nagao, M.;
Kumazawa, K.; Fujita, M. J. Organomet. Chem. 2005, 690, 5383-5388.
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(3) Fujita, M.; Oguro, D.; Miyazawa, M.; Oka, H.; Yamaguchi, K.;
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10.1021/om060843k CCC: $37.00 © 2007 American Chemical Society
Publication on Web 01/06/2007

916 Organometallics, Vol. 26, No. 4, 2007
GoVindaswamy et al.
tate ligand 1,4,7-trithiacyclononane, which coordinates facially
to ruthenium, was used to form a supramolecular cube.9 The
underlying strategy in those examples implies the blocking of
several coordination sites at the metal centers, thus generating
a preorganized arrangement before the formation of the su-
pramolecular assembly.
1,3,5-triazine (4-tpt) and 2,4,6-tris(pyridin-3-yl)-1,3,5-triazine
(3-tpt) ligands.
In a similar manner, cyclopentadienyl or arene ligands can
be used to control the accessibility of coordination sites of an
octahedral metal center.10 The use of these η5 or η6 ligands has
advantages. (i) The aromatic ligand occupies three of the six
coordination sites at the metal center, and the resulting
coordination geometry is pseudo-tetrahedral, allowing a better
control of the synthesis of two- or three-dimensional assemblies.
(ii) The aromatic ligand allows different substituents which can
enhance the solubility or add new properties to the molecular
assembly.
In this paper we report the synthesis and structural charac-
terization of achiral cationic trigonal (arene)ruthenium metallo-
prisms containing bridging chloro ligands.
We have been working with arene ruthenium complexes for
many years,11 and decided to use them as versatile building
blocks in supramolecular chemistry. The triangular prism is the
simplest three-dimensional construction, which involves only
five building blocks: two triangular subunits, and three linear
connecting units:
Results and Discussion
The dinuclear (arene)ruthenium complexes [Ru(η6-arene)(µ-
Cl)Cl]2 (arene ) p-PriC6H4Me, C6Me6) and 2,4,6-tris(pyridin-
4-yl)-1,3,5-triazine (4-tpt) react in water in the presence of
AgO3SCF3 to form in low yield (<25%) the hexanuclear cations
[Ru6(η6-p-PriC6H4Me)6(µ3-4-tpt-κN)2(µ-Cl)6]6+ (3) and [Ru6(η6-
C6Me6)6(µ3-4-tpt-κN)2(µ-Cl)6]6+ (4), respectively (see Scheme
1). However, we found that the yields of 3 and 4 can be
increased significantly by isolating the neutral intermediates
[Ru3(η6-p-PriC6H4Me)3(µ3-4-tpt-κN)Cl6] (1) and [Ru3(η6-C6-
Me6)3(µ3-4-tpt-κN)Cl6] (2), followed by addition of silver triflate
in dichloromethane, which affords 3 and 4 as the triflate salts
in overall yields of about 65%. This significant improvement
in the overall yield can be rationalized in terms of the tpt ligands
being predisposed to form π-π interacting systems, thus
optimizing the formation of a prism over other assemblies.
Despite a molecular weight of 3143.5 for [3][O3SCF3]6 and
3311.8 for [4][O3SCF3]6, the two hexanuclear complexes are
quite soluble in (CH3)2CO, CH3CN, and MeOH and sparingly
soluble in CH2Cl2 and CHCl3.
If these components do not contain stereogenic elements and if
the two planar triangular subunits are perfectly eclipsed, the
triangular prism obtained is achiral. However, a slight deviation
from the eclipsed conformation generates a “double-rosette” type
helicity with ∆ or Λ configuration.12 Recently we have shown
the cationic triangular metallo-prisms [Ru6(η6-arene)6(µ3-4-tpt-
κN)2(µ-C2O4-κO)3]6+ (arene ) p-PriC6H4Me, C6Me6) containing
bridging oxalato ligands to have a double-helical chirality.13
Using a similar approach, we have now synthesized chloro-
bridged metallo-prisms connected by 2,4,6-tris(pyridin-4-yl)-
1
(8) (a) Benkstein, K. D.; Hupp, J. T.; Stern, C. L. J. Am. Chem. Soc.
1998, 120, 12982-12983. (b) Benkstein, K. D.; Hupp, J. T. Mol. Cryst.
Liq. Cryst. 2000, 342, 151-158. (c) Manimaran, B.; Rajendran, T.; Lu,
Y.-L.; Lee, G.-H.; Peng, S.-M.; Lu, K.-L. Eur. J. Inorg. Chem. 2001, 633-
636. (d) Sun, S.-S.; Lees, A. J. Chem. Commun. 2001, 103-104. (e)
Manimaran, B.; Thanasekaran, P.; Rajendran, T.; Liao, R.-T.; Liu, Y.-H.;
Lee, G.-H.; Peng, S.-M.; Rajagopal, S.; Lu, K.-L. Inorg. Chem. 2003, 42,
4795-4797.
The H NMR spectra of 1-4 display similar signal patterns
for the pyridyl protons. Unlike the case for 1, where HR and Hâ
are found at the expected positions (9.3 and 8.5 ppm in CD2-
Cl2), in 3 the signals of HR and Hâ are almost superimposed at
8.7 ppm (see Figure 1). Upon formation of the triangular cationic
prism 3, the HR signal is shifted upfield, whereas the Hâ signal
is shifted downfield. In 3, the signals of the aromatic protons
of the p-cymene ligand are shifted downfield as well as
compared to those of 1 (Figure 1).
(9) Roche, S.; Haslam, C.; Adams, H.; Heath, S. L.; Thomas, J. A. Chem.
Commun. 1998, 1681-1682.
(10) (a) Yan, H.; Su¨ss-Fink, G.; Neels, A.; Stoeckli-Evans, H. J. Chem.
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A.; Mayer, P.; Polborn, K.; Severin, K. Chem., Eur. J. 2001, 7, 3196-
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Fujioka, K.; Arakawa, R. Inorg. Chem. 2002, 41, 6824-6830. (d) Han, W.
S.; Lee, S. W. Dalton Trans. 2004, 1656-1663. (e) Wang, J.-Q.; Ren, C.-
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R. D.; Leung, W.-H. Inorg. Chim. Acta 2006, 359, 978-983.
The infrared spectra of 1-4 are dominated by absorptions
of the coordinated 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine ligand,
which are only slightly shifted as compared to those of the free
ligand (1515 (s), 1374 (s), 794 (s), 641 (s) cm-1).14 In addition
(11) (a) Meister, G.; Rheinwald, G.; Stoeckli-Evans, H.; Su¨ss-Fink, G.
J. Chem. Soc., Dalton Trans. 1994, 3215-3224. (b) Su¨ss-Fink, G.;
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1999, 38, 405-408. (e) Che´rioux, F.; Therrien, B.; Su¨ss-Fink, G. Chem.
Commun. 2004, 204-205. (f) Therrien, B.; Vieille-Petit, L.; Jeanneret-Gris,
J.; Sˇteˇpnicˇka, P.; Su¨ss-Fink, G. J. Organomet. Chem. 2004, 689, 2456-
2463. (g) Govindaswamy, P.; Yennawar, H. P.; Kollipara, M. R. J.
Organomet. Chem. 2004, 689, 3108-3112. (h) Govindaswamy, P.; Carroll,
P. J.; Mozharivskyj, Y. A.; Kollipara, M. R. J. Organomet. Chem. 2005,
690, 885-894. (i) Govindaswamy, P.; Mobin, S. M.; Thone, C.; Kollipara,
M. R. J. Organomet. Chem. 2005, 690, 1218-1225.
(12) (a) Ikeda, A.; Udzu, H.; Zhong, Z.; Shinkai, S.; Sakamoto, S.;
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Hulst, R.; Timmerman, P.; Reinhoudt, D. N. Chem. Eur. J. 2002, 8, 2288-
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D.; Hampel, F.; Bauer, W.; Teichert, M. Chem. Eur. J. 2002, 8, 2679-
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362.

Ruthenium Metallo-Prisms
Organometallics, Vol. 26, No. 4, 2007 917
Figure 1. 1H NMR spectra in CD2Cl2 of 1 (bottom) and 3 (top), showing the pyridyl region of the 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine
ligands and the aromatic region of the p-cymene ligands.
Scheme 1
to the 4-tpt signals, strong absorptions attributed to the triflate
anions (1260 (s), 1030 (s), 639 (s) cm-1 15
are observed in the
infrared spectra of [3][O3SCF3]6 and [4][O3SCF3]6.
The X-ray structure analyses of [3][O3SCF3]6 and [4][O3-
SCF3]6 show strong parallel π stacking interactions between the
aromatic rings of the 4-tpt subunits (Figures 2 and 3). The
centroid‚‚‚centroid distances observed between corresponding
aromatic rings of the π-π interacting systems (3.42-3.64 Å)
are shorter than the theoretical value calculated for this stacking
mode16 but comparable to the 3.46 Å separation observed
between the triazine rings of two independent 4-tpt units in the
crystal packing of [Ir3(η5-C5Me5)3(µ3-4-tpt-κN){η2-S2C2(B10H10)-
κS}3].17 Interestingly, the two 4-tpt units are closer in 4, despite
the slightly longer Ru-Ru separations (3, 3.68 Å; 4, 3.71 Å).
However, these Ru-Ru distances are comparable to those found
in the chloro-bridged dinuclear complexes [Ru(η6-p-PriC6H4-
Me)(µ-Cl)Cl]2 (3.69 Å)18 and [Ru(η6-C6Me6)(µ-Cl)Cl]2 (3.743-
(1) Å).19 In the crystal packing of 3 and 4, no π-stacking
)
(16) Tsuzuki, S.; Honda, K.; Uchimura, T.; Mikami, M.; Tanabe, K. J.
Am. Chem. Soc. 2002, 124, 104-112.
(17) Wang, J.-Q.; Ren, C.-X.; Jin, G.-X. Chem. Commun. 2005, 4738-
4740.
(15) Johnston, D. H.; Shriver, D. F. Inorg. Chem. 1993, 32, 1045-1047.

918 Organometallics, Vol. 26, No. 4, 2007
GoVindaswamy et al.
Figure 2. ORTEP drawing of cation 3 with the hydrogen atoms, acetone molecule, and O3SCF3 anions omitted for clarity.
Figure 3. ORTEP drawing of cation 4 with the hydrogen atoms and O3SCF3 anions omitted for clarity.
interacting systems are observed between independent mol-
ecules. The empty spaces left between the cationic hexanuclear
cations are filled with O3SCF3 anions (Figure 4). Selected bond
lengths and angles are presented in Table 1.
The dinuclear arene ruthenium complexes [Ru(η6-arene)(µ-
Cl)Cl]2 (arene ) p-PriC6H4Me, C6Me6) also react with 2,4,6-
tris(pyridin-3-yl)-1,3,5-triazine (3-tpt) in dichloromethane to give
in excellent yield the trinuclear complexes [Ru3(η6-p-PriC6H4-
Me)3(µ3-3-tpt-κN)Cl6] (5) and [Ru3(η6-C6Me6)3(µ3-3-tpt-κN)-
Cl6] (6), respectively. Subsequent addition of silver triflate to 5
and 6 in dichloromethane affords the hexanuclear cationic prisms
[Ru6(η6-p-PriC6H4Me)6(µ3-3-tpt-κN)2(µ-Cl)6]6+ (7) and [Ru6(η6-
(18) Allardyce, C. S.; Dyson, P. J.; Ellis, D. J.; Salter, P. A.; Scopelliti,
R. J. Organomet. Chem. 2003, 668, 35-42.
(19) McCormick, F. B.; Gleason, W. B. Acta Crystallogr. 1988, C44,
603-605.

Ruthenium Metallo-Prisms
Organometallics, Vol. 26, No. 4, 2007 919
Figure 4. Crystal packing of [3][O3SCF3]6‚(CH3)2CO.
Scheme 2
C6Me6)6(µ3-3-tpt-κN)2(µ-Cl)6]6+ (8), also isolated as their triflate
salts (see Scheme 2). The direct reaction of [Ru(η6-arene)(µ-
Cl)Cl]2 and 3-tpt in the presence of AgO3SCF3, however, does
not afford 7 and 8.20
structure analysis, we determined the molecular structure of [8]-
[O3SCF3]6 (see Figure 6).
The molecular structure of [8][O3SCF3]6 shows, as observed
in [3][O3SCF3]6 and [4][O3SCF3]6, strong parallel π-stacking
interactions between the aromatic rings of the tpt subunits. The
centroid‚‚‚centroid distances observed between corresponding
aromatic rings of the π-π interacting system (range 3.50-3.59
Å) are comparable to those found in cations 3 and 4. Otherwise,
all distances and angles are similar to those found in [3][O3-
SCF3]6 and [4][O3SCF3]6 (see Table 1).
1
The H NMR spectrum of 8 shows, as expected, a well-
organized structure with only one singlet for the methyl protons
of the η6-C6Me6 ligands and four signals for the four different
1
pyridyl protons in the 3-tpt ligands. However, the H NMR
spectrum of 7 shows two sets of signals in an almost 1:1 ratio,
one corresponding to the symmetrical isomer 7a, in which all
pyridyl and p-cymene moieties are equivalent, and a second
one corresponding to the asymmetric isomer 7b, containing three
nonequivalent pyridyl and p-cymene groups (see Figure 5).
Unable to obtain suitable crystals of 7a or 7b for an X-ray
It is obvious from the space-filling representation of cation
8 (Figure 7) that two Ru2(η6-C6Me6)2(µ-Cl)22+ connecting units
cannot fit into the same trigonal segment. However, two Ru2-
(η6-p-PriC6H4Me)2(µ-Cl)2 connecting units can possibly be
2+
accommodated in the same segment, adopting a “face-to-face”
conformation. To confirm this assumption, molecular modeling
using the Hyperchem software was performed.
(20) A complex mixture of unidentified materials was obtained when
the dinuclear (arene)ruthenium complexes [Ru(η6-arene)(µ-Cl)Cl]2 and 3-tpt
were mixed in water in the presence of AgO3SCF3.

920 Organometallics, Vol. 26, No. 4, 2007
GoVindaswamy et al.
Figure 5. Schematic representations of the symmetrical isomer 7a (left) and unsymmetrical isomer 7b (right) with identification of the
trigonal segments (A-C).
Table 1. Selected Bond Lengths and Angles for Cations 3, 4,
and 8
the two 3-tpt ligands. The signal at δ 8.88 ppm is assigned to
the Hγ atoms (of the two equivalent eclipsed pyridyl rings) in
the trigonal segment A of the molecule 7b (see Figure 5), while
the two remaining signals of the Hγ atoms situated in segment
C appear downfield at δ 9.28 and 9.23 ppm. The Hδ protons of
the three pyridyl rings of two equivalent 3-tpt ligands give rise
to two signals at δ 9.64 and 9.57 ppm (ratio 2:1), because the
Hδ atoms, being in the same trigonal segment B, merge at δ
9.64 ppm, while the Hδ atoms in segment A are distinguishable.
The HR and Hâ protons, situated at the periphery of the trigonal
prism, appear as unresolved multiplets centered at 8.85 and 7.70
ppm, respectively.
3
4
8
Distances (Å)
2.128(6)
2.123(6)
2.140(6)
2.122(6)
2.112(6)
2.122(6)
3.6649(8)
3.6783(7)
3.6871(7)
Ru(1)-N(1)
Ru(2)-N(2)
Ru(3)-N(3)
Ru(4)-N(4)
Ru(5)-N(5)
Ru(6)-N(6)
Ru(1)-Ru(2)
Ru(3)-Ru(4)
Ru(5)-Ru(6)
2.127(4)
2.096(5)
2.121(4)
2.105(5)
2.110(4)
2.116(5)
3.7263(8)
3.7060(9)
3.7417(8)
2.104(6)
2.114(6)
2.125(6)
2.111(5)
2.122(6)
2.113(6)
3.7214(9)
3.7085(9)
3.7025(9)
Angles (deg)
97.75(7)
97.62(7)
98.36(6)
98.04(6)
98.52(7)
98.41(7)
1
In the aromatic region of the H NMR spectrum of [7][O3-
Ru(1)-Cl(1)-Ru(2)
Ru(1)-Cl(2)-Ru(2)
Ru(3)-Cl(3)-Ru(4)
Ru(3)-Cl(4)-Ru(4)
Ru(5)-Cl(5)-Ru(6)
Ru(5)-Cl(6)-Ru(6)
98.71(5)
100.78(5)
99.69(5)
99.53(5)
98.05(5)
99.54(5)
99.07(6)
98.44(6)
98.56(6)
98.58(7)
99.01(6)
97.37(6)
SCF3]6 eight doublets of doublets are expected for the p-cymene
protons, two for the symmetrical isomer 7a and six for the
unsymmetrical 7b, but the aromatic resonances are all super-
imposed between δ 5.9 and 6.6 ppm. However, three well-
separated septets for the CH of the isopropyl group of the
p-cymene ligands are observed: one corresponding to 7a and
the remaining two, which show a 2:1 integration ratio, to isomer
7b. Finally, instead of the expected four singlets for the methyl
groups of the p-cymene ligands two badly resolved signals are
observed at δ 2.49 and 2.35 ppm, while a pseudo-multiplet
centered at δ 1.45 ppm is observed for the methyl protons of
the isopropyl substituents, instead of the expected four doublets.
It is well-known that coordinating solvents can cleave chloro-
bridged dinuclear (arene)ruthenium complexes.21 In order to
examine the stability of the chloro-bridged prisms 3, 4, 7, and
The model was built from the molecular structure of cation
8, in which four methyl groups on each hexamethylbenzene
ligand were removed and replaced by hydrogen atoms, giving
rise to the hypothetical cations [Ru6(η6-1,4-Me2C6H4)6(µ3-3-
tpt-κN)2(µ-Cl)6]6+. From this model, which possesses steric
constraint similar to that of the p-cymene derivative, one Ru2-
2+
(η6-1,4-Me2C6H4)2(µ-Cl)2(NC5H4)2 connecting unit was ro-
tated by 180° and reattached to the triazine cores, thus
introducing a second dinuclear connecting unit in the same
trigonal segment. The conformation was optimized by the
Hyperchem software to give the expected unsymmetrical isomer
(7b) without imposing unacceptable distortion on the 3-tpt
ligands or around the diruthenium connecting units (see Figure
8).
1
8 in solution, we recorded the H NMR spectra in various
deuterated solvents (CD2Cl2, (CD3)2CO, CD3CN) with different
coordinating abilities. At room temperature and even elevated
temperature, 1H NMR experiments for 3, 4, 7, and 8 in
dichloromethane-d2 and acetone-d6 showed no signal changes,
indicating the cleavage of the chloro bridges or the presence of
free tpt units. However, in acetonitrile-d3, all complexes show
additional signals attributed to species generated by coordination
of CD3CN ligands, in line with cleavage of the chloro bridges.
In conclusion, we have opened a simple and straightforward
access to chloro-bridged (arene)ruthenium metallo-prisms. These
metallo-prisms show strong π stacking interactions between the
On the basis of these findings, a more detailed NMR study
of [7][O3SCF3]6 using standard 1D and 2D experiments was
carried out, in order to confirm the molecular structures proposed
1
for the two isomers 7a and 7b. As mentioned before, the H
NMR spectrum of 7 displays two distinct sets of signals, which
is particularly obvious in the pyridyl region (see Figure 9). The
first set of signals (2), which shows chemical shifts similar to
those of [8][O3SCF3]6, is assigned to the symmetrical structure
(isomer 7a). The second set of signals (b) is more complex:
three different signals (δ 9.28, 9.23, and 8.88 ppm) can be
identified by a COSY experiment as the Hγ pyridyl protons of
(21) (a) Bennett, M. A.; Smith, A. K. J. Chem. Soc., Dalton Trans. 1974,
233-241. (b) Volland, M. A. O.; Hansen, S. M.; Rominger, F.; Hofmann,
P. Organometallics 2004, 23, 800-816.

Ruthenium Metallo-Prisms
Organometallics, Vol. 26, No. 4, 2007 921
Figure 6. ORTEP drawing of cation 8 with the hydrogen atoms and O3SCF3 anions omitted for clarity.
lished methods. All other reagents were commercially available and
were used as received. UV/visible absorption spectra were recorded
on a Uvikon 930 spectrophotometer using precision cells made of
quartz (1 cm) and exploited with Excel. The 1H and 13C{1H} NMR
spectra were recorded on a Varian Gemini 200 or Bruker AMX
400 spectrometer using the residual protonated solvent as internal
standard. Infrared spectra were recorded as KBr pellets on a Perkin-
Elmer FTIR 1720-X spectrometer. Microanalyses were performed
by the Laboratory of Pharmaceutical Chemistry, University of
Geneva, Geneva, Switzerland.
[Ru3(η6-p-PriC6H4Me)3(µ3-4-tpt-κN)Cl6] (1).25 A mixture of
[Ru(η6-p-PriC6H4Me)(µ-Cl)Cl]2 (100 mg, 0.163 mmol) and 4-tpt
(34 mg, 0.109 mmol) was suspended in CH2Cl2 (20 mL) and stirred
for 3 h at 40 °C. The orange precipitate was filtered, washed with
1
diethyl ether, and dried under vacuum (yield 130 mg, 97%). H
3
NMR (200 MHz, CDCl3): δ (ppm) 9.43 (d, 6H, J ) 6.60 Hz,
3
HR), 8.22 (d, 6H, Hâ), 5.61 (d, 6H, J ) 5.86 Hz, Arp-cym), 5.41
(d, 6H, Arp-cym), 3.06 (sep, 3H, 3J ) 6.96 Hz, CH(CH3)2), 2.20 (s,
9H, CH3), 1.39 (d, 18H, CH(CH3)2). IR (cm-1): 1518 (s), 1371
(s), 806 (s). Anal. Calcd for C48H54N6Cl6Ru3: C, 46.83; H, 4.42;
N, 6.82. Found: C, 46.13; H, 4.24; N, 6.69.
[Ru3(η6-C6Me6)3(µ3-4-tpt-κN)Cl6] (2). A mixture of [Ru(η6-C6-
Me6)(µ-Cl)Cl]2 (100 mg, 0.149 mmol) and 4-tpt (31.1 mg, 0.099
mmol) was suspended in CH2Cl2 (20 mL) and stirred for 3 h at 40
°C. The volume was reduced to 5 mL, and the orange-red solid
was precipitated by addition of diethyl ether and filtered (yield 129
Figure 7. Space-filling representation of cation 8.
tpt units, as demonstrated by 1H NMR spectroscopy and X-ray
structure analyses.
1
3
mg, 98%). H NMR (400 MHz, CDCl3): δ (ppm) 9.21 (d, 6H, J
) 5.60 Hz, HR), 8.42 (d, 6H, Hâ), 2.09 (s, 54H, CH3). 13C{1H}
NMR (100 MHz, CDCl3): δ (ppm) 171.0, 156.6, 143.0, 123.2,
92.1, 16.0. IR (cm-1): 1516(s), 1371(s), 809(s). Anal. Calcd for
C54H66N6Cl6Ru3: C, 49.32; H, 5.06; N, 6.39. Found: C, 49.78; H,
5.04; N, 6.38.
Experimental Section
General Remarks. [Ru(η6-p-PriC6H4Me)(µ-Cl)Cl]2,22 [Ru(η6-
C6Me6)(µ-Cl)Cl]2,23 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine, and 2,4,6-
tris(pyridin-3-yl)-1,3,5-triazine24 were prepared according to pub-
[Ru6(η6-p-PriC6H4Me)6(µ3-4-tpt-κN)2(µ-Cl)6][O3SCF3]6 ([3]-
[O3SCF3]6). A mixture of 1 (100 mg, 0.0812 mmol) and Ag(O3-
(22) Zelonka, R. A.; Baird, M. C. Can. J. Chem. 1972, 50, 3063-3072.
(23) Bennett, M. A.; Huang, T.-N.; Matheson, T. W.; Smith, A. K.
Inorganic Syntheses; Wiley: New York, 1982; Vol. 21, p 74.
(24) Anderson, H. L.; Anderson, S.; Sanders, J. K. M. J. Chem. Soc.,
Perkin Trans. 1 1995, 2231-2246.
(25) Due to solubility problems, no clear 13C NMR spectrum could be
obtained for 1.

922 Organometallics, Vol. 26, No. 4, 2007
GoVindaswamy et al.
Figure 8. Molecular modeling of the unsymmetrical isomer (7b) using the Hyperchem software (two different orientations with mixed
representation).
Figure 9. 1H NMR (200 MHz, acetone-d6) spectrum of cations 7a (2) and 7b (b), showing the pyridyl region of the 2,4,6-tris(pyridin-
3-yl)-1,3,5-triazine ligand.
SCF3) (62.6 mg, 0.243 mmol) in CH2Cl2 (20 cm3) was stirred at
50 °C for 4 h and then filtered. The filtrate was concentrated (3
mL), and diethyl ether was slowly added to precipitate an orange
solid (yield 80 mg, 63%). 1H NMR (400 MHz, acetone-d6): δ (ppm)
8.83 (dd, 12H, J ) 6.80 Hz, J ) 1.16 Hz, HR), 8.79 (dd, 12H,
Hâ), 6.28 (d, 12H, 3J ) 6.60 Hz, Arp-cym), 6.17 (d, 12H, Arp-cym),
3.07 (sep, 6H, 3J ) 6.88 Hz, CH(CH3)2), 2.31 (s, 18H, CH3), 1.46
(d, 36H, CH(CH3)2). 13C{1H} NMR (100 MHz, acetone-d6): δ
(ppm) 170.03, 156.41, 143.99, 125.38, 105.32, 100.56, 83.47 (d),
31.16, 21.85, 17.68. IR (cm-1): 1520 (s), 1376 (s), 1260 (s), 1161
(s), 1030 (s), 810 (s), 639 (s). Anal. Calcd for C102H108Cl6F18N12O18S6-
Ru6: C, 38.97; H, 3.46; N, 5.34. Found: C, 38.83; H, 3.32; N,
5.08.
Crystals suitable for X-ray structure analyses were obtained by
slow diffusion of diethyl ether in an acetone solution of [4][O3-
SCF3]6.
[Ru3(η6-p-PriC6H4Me)3(µ3-3-tpt-κN)Cl6] (5). A mixture of [Ru-
(η6-p-PriC6H4Me)(µ-Cl)Cl]2 (123 mg, 0.200 mmol) and 3-tpt (42
mg, 0.133 mmol) was suspended in CH2Cl2 (20 mL) and stirred
for 3 h at 40 °C. The volume was reduced to 5 mL, and the orange-
red solid was precipitated by addition of diethyl ether, filtered, and
dried under vacuum (yield 85 mg, 52%). 1H NMR (400 MHz, CD2-
3
4
3
Cl2): δ (ppm) 10.46 (s, 3H, Hδ), 9.34 (d, 3H, J ) 5.48 Hz, HR),
9.09 (d, 3H, 3J ) 8.08 Hz, Hγ), 7.67 (dd, 3H, Hâ), 5.77 (d, 6H, 3J
3
) 6.04 Hz, Arp-cym), 5.53 (d, 6H, Arp-cym), 3.07 (sep, 3H, J )
6.92 Hz, CH(CH3)2), 2.08 (s, 9H, CH3), 1.41 (d, 18H, CH(CH3)2).
13C{1H} NMR (100 MHz, CD2Cl2): δ (ppm) 170.1, 158.6, 156.4,
138.0, 132.0, 125.1, 103.4, 97.7, 84.3, 82.4, 31.3, 22.5, 18.5. IR
(cm-1): 1525 (s), 1369 (s), 803 (s). Anal. Calcd for C48H54N6Cl6-
Ru3: C, 46.83; H, 4.42; N, 6.82. Found: C, 46.91; H, 4.42; N,
6.63.
Crystals suitable for X-ray structure analyses were obtained by
slow diffusion of diethyl ether in an acetone solution of [3][O3-
SCF3]6.
[Ru6(η6-C6Me6)6(µ3-4-tpt-κN)2(µ-Cl)6][O3SCF3]6 ([4][O3SCF3]6).
This compound was prepared by the same procedure described
above for 3 using Ag(O3SCF3) (59 mg, 0.228 mmol) and 2 (100
mg, 0.076 mmol) (yield 82 mg, 65%). 1H NMR (400 MHz, acetone-
d6): δ (ppm) 8.81 (dd, 12H, 3J ) 5.24 Hz, 4J ) 1.44 Hz, HR), 8.61
(dd, 12H, Hâ), 2.18 (s, 108H, CH3). 13C{1H} NMR (100 MHz,
acetone-d6): δ (ppm) 170.4, 156.1, 144.1, 126.0, 93.9, 15.3. IR
(cm-1): 1520 (s), 1383 (s), 1259 (s), 1160 (s), 1030 (s), 811 (s),
639 (s). Anal. Calcd for C114H132N12Cl6O18S6F18Ru6: C, 41.34; H,
4.01; N, 5.07. Found: C, 41.38; H, 3.99; N, 4.96.
[Ru3(η6-C6Me6)3(µ3-3-tpt-κN)Cl6] (6). A mixture of [Ru(η6-C6-
Me6)(µ-Cl)Cl]2 (167 mg, 0.25 mmol) and 3-tpt (52 mg, 0.17 mmol)
was suspended in CH2Cl2 (20 mL) and stirred for 3 h at 40 °C.
The volume was reduced to 5 mL, and the orange-red solid was
precipitated by addition of diethyl ether and filtered (yield 170 mg,
1
77%). H NMR (400 MHz, CDCl3): δ (ppm) 10.06 (s, 3H, Hδ),
3
9.13 (d, 3H, J ) 4.04 Hz, HR), 8.94 (d, 3H, Hγ), 7.60 (br, 3H,
Hâ), 2.08 (s, 54H, CH3). 13C{1H} NMR (100 MHz, CDCl3): δ
(ppm) 170.4, 158.5, 155.9, 137.8, 132.3, 125.2, 92.0, 16.0. IR

Ruthenium Metallo-Prisms
Organometallics, Vol. 26, No. 4, 2007 923
Table 2. Crystallographic and Selected Experimental Data For [3][O3SCF3]6‚(CH3)2CO, [4][O3SCF3]6, and [8][O3SCF3]6
[3][O3SCF3]6‚(CH3)2CO
[4][O3SCF3]6
[8][O3SCF3]6
chem formula
formula wt
cryst syst
space group
cryst color and shape
cryst size
a (Å)
C
105H114Cl6F18N12O19Ru6S6
C
114H132Cl6F18N12O18Ru6S6
C
114H132Cl6F18N12O18Ru6S6
3201.56
monoclinic
C2/c
3311.80
monoclinic
P21/n
3311.80
monoclinic
P21/n
orange plate
0.49 × 0.28 × 0.17
76.294(6)
18.2792(11)
19.1459(10)
94.152(7)
26 631(3)
8
orange plate
0.48 × 0.15 × 0.10
23.8695(14)
17.2330(8)
35.282(2)
93.499(7)
14 485.9(14)
4
orange plate
0.24 × 0.18 × 0.07
13.1582(7)
32.575(2)
33.7963(14)
97.394(4)
14 365.6(12)
4
b (Å)
c (Å)
â (deg)
V (Å3)
Z
T (K)
203(2)
1.597
0.966
4.18 < 2θ < 51.90
25 133
14 128
0.0625
0.0546, 0.1390
0.1016, 0.1537
0.902
203(2)
1.519
0.890
4.00 < 2θ < 51.94
28 107
12 233
0.0738
0.0510, 0.1188
0.1069, 0.1321
0.749
173(2)
1.531
0.898
2.50 < 2θ < 50.62
25 651
13 751
0.0918
0.0584, 0.1127
0.1284, 0.1346
0.911
Dc (g cm-3
)
µ (mm-1
scan range (deg)
)
no. of unique rflns
no. of rflns used (I > 2σ(I))
Rint
final R1, wR2 indices (I > 2σ(I))a
R1, wR2 indices (all data)
goodness of fit
max, min ∆F (e Å-3
)
1.887, -3.162
0.601, -0.912
0.677, -1.292
2
2
2
2
2
2
2
a Structures were refined on Fo : wR2 ) [∑[w(Fo - Fc )2]/∑w(Fo )2]1/2, where w-1 ) [∑(Fo ) + (aP)2 + bP] and P ) [max(Fo , 0) + 2Fc ]/3.
(cm-1): 1523 (s), 1367 (s), 805 (s). Anal. Calcd for C54H66N6Cl6-
Ru3: C, 49.32; H, 5.06; N, 6.39. Found: C, 49.75; H, 5.38; N,
6.31.
tion (λ ) 0.710 73 Å) with φ range of 0-200°, increments of 0.7
and 0.6°, respectively, a 2θ range from 4.0 to 52°, and Dmax-Dmin
) 12.45-0.81 Å. A crystal of [Ru6(η6-C6Me6)6(µ3-3-tpt-κN)2(µ-
Cl)6][O3SCF3]6 ([8][O3SCF3]6) was mounted on a Stoe Mark II
image plate diffraction system, using Mo KR graphite-monochro-
mated radiation, an image plate distance of 135 mm, a 2θ range
from 1.7 to 51.6°, and Dmax-Dmin ) 23.99-0.82 Å. The structures
were solved by direct methods using the program SHELXS-97.26
Refinement and all further calculations were carried out using
SHELXL-97.27 In all cases, the H atoms were included in calculated
positions and treated as riding atoms using the SHELXL default
parameters. Examination of the structures with PLATON28 reveals
in [3][O3SCF3]6, [4][O3SCF3]6, and [8][O3SCF3]6 voids between
the anions and cations. Indeed, in [3][O3SCF3]6, one molecule of
acetone could be refined, but more voids were observed. Similarly
in [4][O3SCF3]6 and [8][O3SCF3]6, voids corresponding to solvent
molecules and disordered triflate molecules were found. Therefore,
new data sets corresponding to omission of the missing solvent
and anions were generated with the SQUEEZE algorithm29 and the
three structures were refined to convergence. In some cases,
disordered triflate anions were modeled and fixed at their position
while the well-defined anions were refined anisotropically. How-
ever, in all cases the non-H atoms of the prismatic cations were
refined anisotropically, using weighted full-matrix least squares on
F2. The remaining positive or negative electron densities greater
than 1 e Å-3 were all located next to disordered sulfur atoms.
Crystallographic details are summarized in Table 2. Figures 2, 3,
and 6 were drawn with ORTEP,30 while Figures 4, 7, and 8 were
drawn with MERCURY.31
[Ru6(η6-p-PriC6H4Me)6(µ3-3-tpt-κN)2(µ-Cl)6][O3SCF3]6 ([7]-
[O3SCF3]6). A mixture of 5 (60 mg, 0.05 mmol) and Ag(O3SCF3)
(38 mg, 0.15 mmol) in acetone (20 mL) was stirred at room
temperature for 4 h and then filtered. The filtrate was concentrated
(3 mL), and diethyl ether was slowly added to precipitate an orange
solid (yield 50 mg, 65%). 1H NMR (200 MHz, acetone-d6): δ (ppm)
) 9.67 (d, 6H, 4J ) 1.60 Hz, Hδ) (2), 9.64 (d, 4H, 4J ) 1.60 Hz,
4
Hδ) (b), 9.57 (d, 2H, J ) 1.60 Hz, Hδ) (b), 9.28 (dd, 2H, Hγ)
(b), 9.23 (dd, 2H, Hγ) (b), 8.89-8.82 (m, 20H, Hγ, HR) (b2),
7.84-7.65 (m, 12H, Hâ) (b2), 6.44-6.37 (m, 12H, Arp-cym), 6.34-
623 (m, 12H, Arp-cym), 6.20-6.17 (m, 12H, Arp-cym), 6.07-5.91
(m, 12H, Arp-cym), 3.17-2.99 (m, 12H, CH(CH3)2), 2.49 (s, 18H,
CH3), 2.36 (s, 18H, CH3), 1.54-1.36 (m, 72H, CH(CH3)2). 13C-
{1H} NMR (100 MHz, acetone-d6): δ (ppm) 170.1, 169.3, 168.9,
159.2, 156.9, 154.5, 141.2, 139.4, 134.1, 132.1, 127.6, 123.3, 120.1,
106.0, 103.8, 103.4, 99.5, 99.2, 85.4, 83.7, 83.3, 81.6, 31.2, 31.1,
22.2, 21.5, 19.0, 17.6, 17.5. IR (cm-1): 1525 (s), 1369 (s), 803
(s). Anal. Calcd for C102H108N12Cl6O18S6F18Ru6: C, 38.97; H, 3.46;
N, 5.34. Found: C, 38.65; N, 3.37; N, 5.22.
[Ru6(η6-C6Me6)6(µ3-3-tpt-κN)2(µ-Cl)6][O3SCF3]6 ([8][O3SCF3]6).
A mixture of 6 (120 mg, 0.091 mmol) and Ag(O3SCF3) (70 mg,
0.27 mmol) in CH2Cl2 (20 mL) was stirred at 50 °C for 4 h and
then filtered. The filtrate was concentrated (3 mL), and diethyl ether
was slowly added to precipitate an orange solid (yield 120 mg,
1
4
79%). H NMR (400 MHz, acetone-d6): δ (ppm) 9.51 (d, 6H, J
3
3
) 1.94 Hz, Hδ), 8.85 (dd, 6H, J ) 4.60 Hz, HR), 8.69 (d, 6H, J
) 5.64 Hz, Hγ), 7.99 (dd, 6H, Hâ), 2.22 (s, 108H, C6Me6). 13C-
{1H} NMR (100 MHz, acetone-d6): δ (ppm) 169.1, 158.9, 154.1,
139.8, 132.6, 129.0, 94.0, 15.5. IR (cm-1): 1636 (s), 1531 (s), 1384
(s), 1260 (s), 1161 (s), 1032 (s), 639 (s). Anal. Calcd for
The files CCDC-600474 (for [Ru6(η6-p-PriC6H4Me)6(µ3-4-tpt-
κN)2(µ-Cl)6][O3SCF3]6‚(CH3)2CO), CCDC-600475 (for [Ru6(η6-C6-
Me6)6(µ3-4-tpt-κN)2(µ-Cl)6][O3SCF3]6), and CCDC-619336 (for
[Ru6(η6-C6Me6)6(µ3-3-tpt-κN)2(µ-Cl)6][O3SCF3]6) contain the supple-
mentary crystallographic data for this paper. These data can be
C114H132N12Cl6O18S6F18Ru6: C, 41.34; H, 4.01; N, 5.07. Found:
C, 41.80; H, 3.95; N, 5.05.
(26) Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467-473.
(27) Sheldrick, G. M. SHELXL-97; University of Go¨ttingen, Go¨ttingen,
Germany, 1999.
(28) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13.
(29) van der Sluis, P.; Spek, A. L. Acta Crystallogr. 1990, A46, 194-
201.
(30) Farrugia, L. J. J. Appl. Crystallogr. 1997, 30, 565.
(31) Bruno, I. J.; Cole, J. C.; Edgington, P. R.; Kessler, M.; Macrae, C.
F.; McCabe, P.; Pearson, J.; Taylor, R. Acta Crystallogr. 2002, B58, 389-
397.
Crystals suitable for X-ray structure analyses were obtained by
slow diffusion of diethyl ether in an acetone solution of [8][O3-
SCF3]6.
X-ray Crystallographic Study. Crystals of [Ru6(η6-p-PriC6H4-
Me)6(µ3-4-tpt-κN)2(µ-Cl)6][O3SCF3]6‚(CH3)2CO ([3][O3SCF3]6) and
[Ru6(η6-C6Me6)6(µ3-4-tpt-κN)2(µ-Cl)6][O3SCF3]6 ([4][O3SCF3]6) were
mounted on a Stoe image plate diffraction system equipped with a
φ circle goniometer, using Mo KR graphite-monochromated radia-

924 Organometallics, Vol. 26, No. 4, 2007
GoVindaswamy et al.
obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
(or from the Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB2 1EZ, U.K.; fax, (internat.) +44-1223/336-
033; e-mail, deposit@ccdc.cam.ac.uk).
and Johnson Matthey Research Centre for a generous loan of
ruthenium chloride hydrate.
Supporting Information Available: Figures giving selected
1H NMR spectra and CIF files giving X-ray data for 3, 4, and 8.
This material is available free of charge via the Internet at
http://pubs.acs.org.
Acknowledgment. P.G. acknowledges financial support
from the Swiss Federal Commission for Scholarship (FCS). We
thank Professor H. Stoeckli-Evans for access to X-ray facilities
OM060843K