Reactions of pyridyl side chain functionalized indenes with Ru 3(CO)12

Article abstract of DOI:10.1002/ejic.200701186

Reactions of the pyridyl side chain functionalized indenes 3-R-C ₉H₇ [R = (C₅H₄N)CH ₂CMe₂ (1), (MeC₅H₃N)CH ₂CMe₂ (2), (C₅H₄

Full text of DOI:10.1002/ejic.200701186

FULL PAPER
DOI: 10.1002/ejic.200701186
Reactions of Pyridyl Side Chain Functionalized Indenes with Ru3(CO)12
Dafa Chen,[a] Shansheng Xu,[a] Haibin Song,[a] and Baiquan Wang*[a,b]
Keywords: Ruthenium / Carbonyl ligands / C–H activation / Coordination modes / Arene ligands / Cluster compounds
Reactions of the pyridyl side chain functionalized indenes 3-
R-C9H7 [R = (C5H4N)CH2CMe2 (1), (MeC5H3N)CH2CMe2 (2),
(C5H4N)CH2 (6)] with Ru3(CO)12 in refluxing xylene gave the
facial coordinated indenyl cluster [µ3-η5:η2:η2-(C5H3N)-
refluxing heptane, the ionic clusters {[(C5H4N)CH2Me2C-
–
(C9H6)]Ru(CO)2}+[HRu6(CO)18
]
(19), [(C5H4N)CH2Me2C-
–
(C9H8)]+[HRu6(CO)18
]
(20), and complex 8 or ionic clusters
{[(MeC5H3N)CH2Me2C(C9H6)]Ru(CO)2}+[HRu6(CO)18
]
(21)
–
CH2Me2C(C9H6)]Ru4(µ3-CO)(CO)7 (8), the syn-η5:η6-coordi- and [(MeC5H3N)CH2Me2C(C9H8)]+[HRu6(CO)18
]
(22) were
–
nated indenyl cluster [µ-η5:η6-(MeC5H3N)CH2CMe2(C9H6)-
Ru2(CO)3]2 (10), and the η1:η2-coordinated indenyl complex
[η2-(C5H3N)CH2(C9H7)][η1:η2-(C5H4N)CH2(C9H6)]Ru2(CO)4
(18), respectively, in addition to the normal diruthenium com-
plexes [(η5-RC9H6)Ru(CO)]2(µ-CO)2 [R = (C5H4N)CH2CMe2
(7), (MeC5H3N)CH2CMe2 (9), (C5H4N)CH2 (17)]. When the
pyridyl side chains were replaced by other bulky groups [R
= tBu (3), PhCH2Me2C (4), (C9H6N)CH2Me2C (5)], the similar
syn-η5:η6-coordinated indenyl clusters 12, 14, and 16 were
also obtained. When 1 or 2 were treated with Ru3(CO)12 in
obtained. Similar treatment of 5 or 6 with Ru3(CO)12 in re-
fluxing heptane gave the ionic clusters [(C9H6N)CH2Me2C-
–
(C9H8)]+[HRu6(CO)18
]
(23) or {[η3-(C5H4N)CH(C9H7)][η2-
(C5H4N)CH2(C9H7)]Ru(CO)}+[HRu6(CO)18
]
(24), respec-
–
tively, in addition to complex 18 in the latter case. The molec-
ular structures of 8, 9, 10, 14, 17, 18, 21, 22, and 24 were
determined by X-ray diffraction analysis.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
Introduction
Results and Discussion
Reaction of 1 with Ru3(CO)12 in Xylene
Indenyl metal complexes have received increasing atten-
tion due to the diverse and flexible hapticities and the en-
When 1[9] was treated with Ru3(CO)12 in refluxing xylene
hanced reactivities both in stoichiometric reactions and ca- for 5 h, the α-C–H bond of the pyridyl group activated
talysis;[1] this is sometimes referred to as the indenyl effect.[2] product 8 was obtained in 29% yield, in addition to the
More than 10 coordination modes have been found for the normal diruthenium complex 7 (14%) (Scheme 1). Al-
indenyl ligand.[3–6] The donor side chain functionalized cy- though xylene was used as the solvent, no product resulting
clopentadienyl or indenyl ligands have usually been used to from the reaction of Ru3(CO)12 with xylene was detected.[10]
form intramolecular coordination to a Lewis acidic metal The lower yields can be attributed to the significant decom-
center or to construct oligonuclear metal complexes, which position of Ru3(CO)12, which resulted in a large amount of
usually show different structures and reactivities.[7] In our dark solid that was not soluble in common solvents.
previous work, we studied the reactions of pyridyl side
chain functionalized cyclopentadienes with metal carbonyl
and obtained some novel intramolecular C–H activated
products.[8] By considering the various coordination modes
between the indenyl group and the metal atoms, we further
studied the reactions of pyridyl side chain functionalized
indenes with Ru3(CO)12, and a series of indenyl ruthenium
complexes with different coordination modes were ob-
tained.
Scheme 1.
[a] State Key Laboratory of Elemento-Organic Chemistry, College
of Chemistry, Nankai University,
The IR spectrum of 7 shows terminal and bridging car-
bonyl group absorptions at 1957 and 1770 cm–1, which is
indicative of the symmetrical structure (trans). The IR spec-
trum of 8 shows eight carbonyl group absorptions at 2034–
1851 cm–1. Single-crystal X-ray diffraction analysis showed
that complex 8 is an indenyl tetranuclear ruthenium cluster
Tianjin 300071, People’s Republic of China
Fax: +86-22-23504781
E-mail: bqwang@nankai.edu.cn
[b] Key Laboratory of Organometallic Chemistry, Shanghai Insti-
tute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, People’s Republic of China
1854
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 1854–1864

Reactions of Pyridyl Side Chain Functionalized Indenes with Ru3(CO)12
(Figure 1). There are two crystallographically independent asymmetrically bonding with Ru(5), Ru(6), and Ru(8) [Ru–
molecules, 8A and 8B, in the unit cell. In both of the two C: 2.086(5), 2.464(6), 2.162(5) Å, respectively] in 8B, and a
molecules, the metal framework consists of a tetrahedron µ-CO [C(6)–O(6)] ligand that bridges Ru(1) and Ru(4) in
with the indenyl group lying over one of the triangular faces 8A. The distances of Ru(6)–C(37) [2.238(4) Å], Ru(6)–C(38)
in η5:η2:η2 modes. The η5-indenyl-coordinated Ru(3) or [2.238(4) Å], Ru(2)–C(19) [2.199(5) Å], and Ru(2)–C(20)
Ru(7) center is coordinated to the N atom of the pyridyl [2.245(5) Å] are similar, which supports the η2 coordination
group. The Ru(4) or Ru(8) is bonded with the α-C of the mode. However, the distances of Ru(5)–C(36) [2.462(4) Å]
pyridyl unit through C–H activation. Each of the indenyl and Ru(1)–C(18) [2.608 Å] are much longer than those of
ligands donates a total of 9 electrons, so the valence elec- Ru(6)–C(35) [2.205(5) Å] and Ru(1)–C(17) [2.162(5) Å],
trons of 8 are 62, which is in accord with the theoretical which provides evidence for the twisted η2 coordination.
value.[11] There is a µ3-CO ligand [C(14)–O(14)] that is The Ru(1)–C(18) distance is even longer than those of
Ru(2)–C(18) [2.467(5) Å], which is close to η1:η3 coordina-
tion. It agrees with the shorter distance of C(18)–C(19)
[1.412(8) Å] than those of C(17)–C(18) [1.435(7) Å]. The
greatly twisted η2:η2 coordination might be due to packing
effects. Although there are two isomers in the unit cell, the
1H NMR spectrum of 8 shows the existence of only one
isomer. This indicates that they may exist as one form in
solution; however, the fact that a rapid fluxional process
exists cannot be excluded.[3c,12] Only a few complexes with
µ3-η5:η2:η2-bonding indenyl ligands have been reported for
ruthenium and osmium clusters,[5] so complex 8 is another
example of this kind of complex.
Considering the similarity of iron with ruthenium, the
reaction of 1 with Fe(CO)5 was also done but TLC analysis
showed no product except for the decomposition of Fe-
(CO)5, possibly due to the poor reactivity of Fe(CO)5.
Reactions of 2–5 with Ru3(CO)12 in Xylene
Similarly, reaction of 2 with Ru3(CO)12 gave the normal
diruthenium complex 9 (13%) and a tetranuclear complex
10 (26%) (Scheme 2). The IR spectrum of 9 shows terminal
and bridging carbonyl group absorptions at 1957 and
1774 cm–1, similar to that of 7. X-ray analysis confirms that
9 is a trans isomer (Figure 2). The IR spectrum of 10 shows
only three terminal carbonyl group absorptions at 1962,
1918, and 1863 cm–1. X-ray analysis shows that 10 is a Ci
symmetrical tetranuclear complex with a flat butterfly
metal framework and two indenyl ligands (Figure 3). The
Ru–Ru distances (2.7266 to 2.8223 Å) are much shorter
than those in Ru4(CO)13(µ-PPh2)2 (2.9704–3.1776 Å).[13]
Figure 1. Molecular structure of 8. Two crystallographically inde-
pendent molecules in the unit cell are shown as 8A (top) and (8B)
(bottom). Selected bond lengths [Å]: Ru(1)–Ru(4) 2.7520(13),
Ru(1)–Ru(3) 2.8074(16), Ru(1)–Ru(2) 2.8213(13), Ru(2)–Ru(4)
2.7568(14), Ru(2)–Ru(3) 2.9303(12), Ru(3)–Ru(4) 2.7492(13),
Ru(1)–C(17) 2.162(5), Ru(2)–C(18) 2.467(5), Ru(2)–C(19) 2.199(5),
Ru(2)–C(20) 2.245(5), Ru(3)–N(1) 2.098(4), Ru(4)–C(32) 2.062(4),
Ru(5)–C(35) 2.205(5), Ru(5)–C(36) 2.462(4), Ru(5)–C(14) 2.086(5),
Ru(6)–C(14) 2.464(6), Ru(6)–C(37) 2.238(4), Ru(6)–C(38) 2.238(4),
Ru(8)–C(14) 2.162(5), Ru(8)–C(50) 2.052(5), Ru(7)–N(2) 2.097(4),
C(17)–C(18) 1.435(7), C(17)–C(25) 1.444(6), C(18)–C(19) 1.412(8),
C(19)–C(20) 1.396(7), C(20)–C(21) 1.435(6), C(21)–C(25) 1.466(6),
C(35)–C(36) 1.408(7), C(35)–C(43) 1.455(6), C(36)–C(37) 1.420(7),
C(37)–C(38) 1.399(7), C(38)–C(39) 1.443(6), C(39)–C(43) 1.465(6). Scheme 2.
Eur. J. Inorg. Chem. 2008, 1854–1864
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D. Chen, S. Xu, H. Song, B. Wang
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Figure 2. ORTEP diagram of 9. Selected bond lengths [Å]: Ru(1)–Ru(1A) 2.7443(13).
The pyridyl groups only act as substituents and do not co- (CO)12,[14] which leads to the formation of 8, in which the
ordinate with the Ru atoms. The most noticeable structural indenyl ligands are bound in a facial η5:η2:η2 bonding
feature of 10 is the bridging indenyl ligands, which coordi- mode.
nate with two ruthenium atoms in a syn-η5:η6-facial fash-
Considering that the pyridyl groups of 10 do not coordi-
ion. Bimetallic complexes with indenyl bridging facial li- nate with the Ru atoms, reactions of 3–5, in which the pyr-
gands are scarce,[2,3] and only a few such complexes have idyl side chains were replaced by other bulky substituents
ligands that bridge in a syn-facial fashion; therefore, com- [tBu, PhCH2Me2C, and (C9H6N)CH2Me2C (C9H6N = 2-
plex 10 is a new example containing syn-η5:η6 bonding in- quinolyl)], with Ru3(CO)12 were also done, and complexes
denyl ligands.
with similar structures were obtained (Scheme 2). Single-
crystal X-ray analysis showed that complex 14 also contains
two syn-η5:η6 bonding indenyl groups, similar to that ob-
served in 10 (Figure 4). This indicates that the steric effect
of the bulky substituent in the 1-position of the indenyl ring
Figure 3. Molecular structure of 10. Selected bond lengths [Å]:
Ru(1)–Ru(1A) 2.7266(8), Ru(1)–Ru(2A) 2.7354(6), Ru(1)–Ru(2)
2.8223(6), Ru(1)–C(4) 2.419(5), Ru(1)–C(5) 2.224(5), Ru(1)–C(6)
2.234(5), Ru(1)–C(7) 2.296(5), Ru(1)–C(8) 2.367(5), Ru(1)–C(9)
2.464(5), Ru(2)–C(4) 2.499(4), Ru(2)–C(9) 2.573(4), Ru(2)–C(10)
2.319(5), Ru(2)–C(11) 2.210(5), Ru(2)–C(12) 2.282(5), C(4)–C(5)
1.431(6), C(4)–C(9) 1.450(6), C(5)–C(6) 1.421(7), C(6)–C(7)
1.398(7), C(7)–C(8) 1.407(7), C(8)–C(9) 1.415(6).
Figure 4. ORTEP diagram of 14. Selected bond lengths [Å]: Ru(1)–
Ru(1A) 2.7461(7), Ru(1)–Ru(2A) 2.8233(6), Ru(1)–Ru(2) 2.7287(5),
Ru(1)–C(6A) 2.472(3), Ru(1)–C(7A) 2.370(4), Ru(1)–C(8A)
2.312(4), Ru(1)–C(9A) 2.245(3), Ru(1)–C(10A) 2.204(4), Ru(1)–
C(11A) 2.408(3), Ru(2)–C(4) 2.205(4), Ru(2)–C(5) 2.314(4), Ru(2)–
C(6) 2.562(3), Ru(2)–C(11) 2.499(3), Ru(2)–C(12) 2.269(4), C(6)–
C(7) 1.408(5), C(6)–C(11) 1.455(5), C(7)–C(8) 1.398(5), C(8)–C(9)
The only difference between 2 and 1 is the methyl substit-
uent at the α-position of the pyridyl group. The α-C–H
bond of the pyridyl ring in 1 can be activated by Ru3- 1.394(5), C(9)–C(10) 1.412(5), C(10)–C(11) 1.436(5).
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Reactions of Pyridyl Side Chain Functionalized Indenes with Ru3(CO)12
Figure 5. ORTEP diagram of 17. Selected bond lengths [Å]: Ru(1)–Ru(1A) 2.7389(15).
may promote the formation of the syn-η5:η6 bonded in-
denyl tetranuclear ruthenium complexes. In contrast, reac-
tions of 1-ferrocenyl, 1-CH2CH2C9H7, or 1,2,3-trimethyl-
substituted indenes with Ru3(CO)12 only gave the normal
η5-indenyl diruthenium complexes.[15,1c] Reaction of 2-
phenyl-substituted indene with Ru3(CO)12 also gave the η5-
indenyl diruthenium complex, in addition to a heptaruthen-
ium cluster.[16]
Reaction of 6 with Ru3(CO)12 in Xylene
Thermal treatment of Ru3(CO)12 with 6,[17] in which a
short pyridyl side chain with smaller steric effects was intro-
duced, gave the cis diruthenium complex 17 (3%) (Figure 5)
and complex 18 (24%) (Scheme 3). Different with trans
complexes 7 and 9, cis complex 17 shows two terminal and
two bridging carbonyl group absorptions at 1973 (s), 1936
(s), 1812 (m), and 1774 (s) cm–1 in its IR spectrum. The IR
Figure 6. Molecular structure of 18. Selected bond lengths [Å]:
spectrum of 18 shows four terminal carbonyl group absorp-
tions at 2000–1916 cm–1. Single-crystal X-ray diffraction
analysis shows that 18 is a diruthenium complex with two
ligands (Figure 6). Each of the two N atoms coordinates
with one Ru atom. One of the ligands is cyclometalated and
coordinates with Ru(2) and Ru(1) in a η1:η2 mode. The
bond lengths of C(20)–C(28) [1.464(4) Å] and C(27)–C(28)
[1.481(4) Å] are significantly shorter than C(5)–C(6)
[1.527(5) Å] and C(6)–C(7) [1.513(5) Å], which suggests that
there are similarities between the η1:η2- and η3-coordina-
tion modes. The other ligand coordinates with Ru(1) in a
η2 mode. The α-C of the pyridyl ring is bonded to the Ru(2)
atom by C–H activation.
Ru(1)–Ru(2) 2.9448(5), Ru(1)–N(1) 2.088(2), Ru(1)–C(5) 2.228(3),
Ru(1)–C(13) 2.256(3), Ru(1)–C(20) 2.371(3), Ru(1)–C(21) 2.323(3),
Ru(2)–N(2) 2.188(2), Ru(2)–C(28) 2.211(3), Ru(2)–C(19) 2.044(3),
C(5)–C(6) 1.527(5), C(5)–C(13) 1.421(4), C(20)–C(21) 1.414(4),
C(20)–C(28) 1.464(4).
Reactions of 1, 2, and 5 with Ru3(CO)12 in Heptane
The high temperature of refluxing xylene might cause
significant decomposition of Ru3(CO)12, so heptane was
chosen as the solvent instead. When 1 or 2 was treated with
Ru3(CO)12 in refluxing heptane, ionic clusters 19 (12%), 20
(34%), and complex 8 (5%) or ionic clusters 21 (13%) and
22 (25%) were obtained, respectively (Scheme 4). The total
yield was merely a little higher than that in xylene, but dif-
ferent products were formed. When 5 was treated with
Ru3(CO)12, only compound 23 (15%) was obtained. Com-
pounds 19 and 21 show similar three carbonyl group ab-
sorptions at 2050–1954 cm–1 in their IR spectra and have
similar 1H NMR signals, which indicates that they have
similar structures. X-ray diffraction analysis showed that 21
is an ionic cluster (Figure 7). The cation is a η5-indenyl ru-
thenium complex with intramolecular coordination of the
pyridyl group. The anion [HRu6(CO)18]– was discovered be-
fore.[14] Compounds 20, 22, and 23 have similar structures,
Scheme 3.
Eur. J. Inorg. Chem. 2008, 1854–1864
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D. Chen, S. Xu, H. Song, B. Wang
FULL PAPER
Scheme 4.
which was evidenced by their similar 1H NMR spectra. The ter (Figure 8). The anion [HRu6(CO)18]– is the same as that
IR spectra of 20 and 23 showed two carbonyl group absorp- in 21, but the cation is a pyridinium ion with a spirocyclic
tions at 2012 and 1953 and at 2012 and 1954 cm–1, respec- structure. It seems that the formation of 20, 22, and 24 may
tively, whereas the IR spectrum of 22 showed four carbonyl involve cyclometalation, followed by reductive elimination
group absorptions at 2054, 2018, 1998, and 1987 cm–1. X- (Scheme 5).[18]
ray diffraction analysis showed that 22 is also an ionic clus-
Scheme 5.
Reaction of 6 with Ru3(CO)12 in Heptane
When 6 was treated with Ru3(CO)12 in refluxing heptane,
red ionic complex 24 was obtained, in addition to complex
18 (Scheme 6). The cation of 24 contains a Ru atom and
Figure 7. Structure of the cation of 21.
two ligands with intramolecular coordination of the pyridyl
group. One ligand coordinates with the Ru atom in a η3
mode, whereas the other coordinates in a η2 mode (Fig-
ure 9). Again, the anion is [HRu6(CO)18]–.
Scheme 6.
From the above results, we can see that the reaction sol-
vents have significant effects on the formation of the prod-
ucts. Similar phenomenon was also reported in the reac-
Figure 8. Structure of the cation of 22.
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Eur. J. Inorg. Chem. 2008, 1854–1864

Reactions of Pyridyl Side Chain Functionalized Indenes with Ru3(CO)12
1H NMR Spectra Analysis
1
The H NMR spectra of the normal η5-coordinated in-
denyl diruthenium complexes 7, 9, 11, 13, 15, and 17 are
similar (Table 1). They all show three or four groups of
peaks at 7.77–6.34 ppm for the C6-ring protons of the in-
denyl ligand and two doublets or broad singlets at 5.61–
4.44 ppm for the C5-ring protons of the indenyl ligand.
However, the chemical shifts of the benzo ring protons of
11 and 13 (7.77–6.65 ppm) are shifted downfield relative to
those of the pyridyl or quinolyl side chain functionalized
indenyl complexes 7, 9, 15, and 17 (7.33–6.34 ppm), which
is indicative of the effects of the N-heterocyclic side chains.
The α,β-protons of the indenyl ring system and the CH2
protons in the side chains were generally split into two char-
acteristic doublets. It is easy to distinguish them by the
1
large coupling constant (J2) of the CH2 protons. The H
NMR spectrum of 17 showed two groups of characteristic
doublets for the five-membered protons of the indenyl unit,
which indicates the existence of only one isomer. Dinuclear
η5-dienylruthenium complexes are usually obtained as mix-
tures of cis and trans isomers or as single trans isomers
(such as 7 and 9). There is only one example of a 2-phen-
Figure 9. Structure of the cation of 24.
tions of Ru3(CO)12 and Os3(CO)12.[5a,5b,5d,16,19] The solvent ylindenyl diruthenium complex [(η5-C9H6Ph)Ru(CO)(µ-
effect for this kind of thermal reaction is partly decided CO)]2 in which the cis meso isomer was obtained and char-
by the reaction temperature. When ligand precursor 2 was acterized by X-ray diffraction analysis.[16] The reason why
treated with Ru3(CO)12 in heptane at 140 °C, complex 10 complex 17 exists as a single cis meso isomer is still not very
was also isolated, in addition to 21 and 22. However, no clear. It seems that the existence of a picolyl (or phenyl)
relationship between these complexes was found. So, the substituent on the indenyl ring may stabilize the cis meso
nature of the solvents plays the determined role in the for- isomer and promote its formation.
mation of the products. The aromatic solvent, such as xy-
lene, may act as an electron donor to coordinate with the denyl complexes 8, 10, 12, 14, and 16 in their H NMR
The most noticeable feature of the facial coordinated in-
1
metal and to promote or change the reactions.
spectra is that nearly all resonances are shifted upfield rela-
1
Table 1. H NMR data of complexes 7, 9, 11, 13, 15, and 17 (in CDCl3, ppm).
Pyridyl H, quinolyl H, or C6-ring H of indenyl
C5-ring H of indenyl
Other H
7
9
8.42 (d, J = 4.9 Hz, 2 H)
7.66 (d, J = 8.7 Hz, 2 H)
7.39–7.28 (m, 4 H), 7.21–7.15 (m, 2 H)
7.04–6.98 (m, 4 H), 6.46 (d, J = 7.8 Hz, 2 H)
7.58 (d, J = 8.7 Hz, 2 H), 7.34 (t, 2 H)
7.15 (m, 4 H), 7.00 (d, J = 8.4 Hz, 2 H)
6.86 (br. s, 2 H), 6.34 (d, J = 7.6 Hz, 2 H)
5.19 (d, J = 3.0 Hz, 2 H)
4.48 (d, J = 3.0 Hz, 2 H)
3.26 (d, J = 13.0 Hz, 2 H, CH2)
3.13 (d, J = 13.0 Hz, 2 H, CH2)
1.84 (s, 6 H, CMe2)
1.52 (s, 6 H, CMe2)
3.28–2.98 (m, 4 H, CH2)
2.33 (s, 6 H, PyMe)
5.20 (br. s, 2 H)
4.49 (br. s, 2 H)
1.85 (s, 6 H, CMe2)
1.52 (s, 6 H, CMe2)
1.59 (s, 18 H, CMe3)
11
13
7.77 (d, J = 8.5 Hz, 2 H), 7.33–7.19 (m, 4 H)
6.90 (d, J = 8.3 Hz, 2 H)
7.71(d, J = 8.6 Hz, 2 H), 7.38 (t, 2 H)
7.24–7.02 (m, 10 H)
5.49 (d, J = 3.1 Hz, 2 H)
4.52 (d, J = 3.1 Hz, 2 H)
5.07 (d, J = 3.1 Hz, 2 H)
4.46 (d, J = 3.1 Hz, 2 H)
3.11 (d, J = 13.1 Hz, 2 H, CH2)
2.92 (d, J = 13.1 Hz, 2 H, CH2)
1.82 (s, 6 H, CMe2)
6.65 (d, J = 6.4 Hz, 4 H)
1.42 (s, 6 H, CMe2)
15
7.87 (d, J = 8.4 Hz, 2 H)
7.74 (d, J = 8.4 Hz, 2 H)
7.69–7.60 (m, 6 H), 7.45 (t, 2 H)
7.33 (t, 2 H), 7.11 (t, 2 H)
5.13 (d, J = 3.0 Hz, 2 H)
4.44 (d, J = 3.0 Hz, 2 H)
3.46 (d, J = 12.4 Hz, 2 H, CH2)
3.30 (d, J = 12.4 Hz, 2 H, CH2)
1.91 (s, 6 H, CMe2)
1.56 (s, 6 H, CMe2)
7.01 (d, J = 8.4 Hz, 2 H)
6.56 (d, J = 8.4 Hz, 2 H)
17
8.51 (d, J = 4.8 Hz, 2 H), 7.58 (t, 2 H)
7.40 (d, J = 7.8 Hz, 2 H), 7.33–7.22 (m, 4 H)
7.18 (d, J = 7.8 Hz, 2 H), 7.12 (t, 2 H)
7.05 (d, J = 7.8 Hz, 2 H)
5.61 (d, J = 3.0 Hz, 2 H)
5.19 (d, J = 3.0 Hz, 2 H)
4.32 (d, J = 15.3 Hz, 2 H, CH2)
4.21 (d, J = 15.3 Hz, 2 H, CH2)
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Other H
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1
Table 2. H NMR data of complexes 8, 10, 12, 14, 16, and 18 (in CDCl3, ppm).
Pyridyl H, quinolyl H or C6-ring H of indenyl
C5-ring H of indenyl
8
7.47 (d, J = 7.5 Hz, 1 H), 7.07 (t, 1 H)
6.51 (d, J = 7.5 Hz, 1 H)
5.96 (d, J = 3.0 Hz, 1 H), 5.14 (m, 1 H)
3.52 (d, J = 3.0 Hz, 1 H), 3.35 (m, 1 H)
7.37 (t, 2 H), 6.94 (d, J = 7.7 Hz, 2 H)
6.66 (d, J = 7.6 Hz, 2 H)
5.90 (d, J = 5.3 Hz, 1 H)
4.55 (d, J = 5.3 Hz, 1 H)
2.83(d, J = 14.2 Hz, 1 H, CH2)
2.32 (d, J = 14.2 Hz, 1 H, CH2)
1.60 (s, 3 H, CMe2)
0.56 (s, 3 H, CMe2)
2.87 (m, 4 H, Py-CH2)
1.20 (s, 6 H, CMe2)
10
5.25 (d, J = 6.4 Hz, 2 H)
3.51 (d, J = 6.4 Hz, 2 H)
6.28 (d, J = 3.0 Hz, 2 H)
6.16 (t, 2 H), 5.54 (t, 2 H)
0.89 (s, 6 H, CMe2)
2.41 (s, 6 H, Py-Me)
3.78 (d, J = 2.6 Hz, 2 H)
6.49 (d, J = 2.9 Hz, 2 H)
6.23 (t, 2 H), 5.77 (t, 2 H)
3.84 (d, J = 3.2 Hz, 2 H)
7.21–7.15 (m, 6 H), 6.87–6.83(m, 4 H)
6.23 (d, J = 2.9 Hz, 2 H)
6.18 (t, 2 H), 5.60 (t, 2 H)
12
14
5.28 (d, J = 6.10 Hz, 2 H)
3.93 (d, J = 6.10 Hz, 2 H)
1.07 (s, 18 H, CMe3)
5.28 (d, J = 6.09 Hz, 2 H)
3.63 (d, J = 6.09 Hz, 2 H)
2.79 (d, J = 12.9 Hz, 2 H, CH2)
2.67 (d, J = 12.9 Hz, 2 H, CH2)
1.11 (s, 6 H, CMe2)
3.80 (d, J = 2.9 Hz, 2 H)
7.95–7.87 (m, 4 H), 7.76 (d, J = 8.6 Hz, 2 H)
7.68 (t, 2 H), 7.51 (t, 2 H)
6.96 (d, J = 8.4 Hz, 2 H)
6.28 (d, J = 2.9 Hz, 2 H)
6.04 (t, 2 H, Ar-H) 5.26–5.19 (m, 2 H)
3.75 (d, J = 2.3 Hz, 2 H)
8.84 (d, J = 5.1 Hz, 1 H)
8.01 (d, J = 7.5 Hz, 1 H), 7.65 (m, 1 H)
7.44 (t, 1 H), 7.40–7.27 (m, 3 H)
7.40–7.27 (m, 1 H), 7.15 (m, 2 H)
6.76 (m, 1 H), 6.68 (m, 1 H)
6.29 (t, 1 H), 6.19 (d, J = 7.6 Hz, 1 H)
5.98 (d, J = 7.4 Hz, 1 H)
0.86 (s, 6 H, CMe2)
16
18
5.26–5.19 (m, 2 H)
3.40 (d, J = 5.7 Hz, 2 H)
3.15 (d, J = 12.1 Hz, 2 H, CH2)
3.04 (d, J = 12.1 Hz, 2 H, CH2)
1.25 (s, 6 H, CMe2)
0.95 (s, 6 H, CMe2)
5.29 (d, J = 4.1 Hz, 1 H)
3.96 (m, 2 H)
3.88 (d, J = 6.0 Hz, 1 H)
3.60–3.51 (m, 1 H)
4.69 (d, J = 17.0 Hz, 1 H, CH2)
3.81 (d, J = 17.0 Hz, 1 H, CH2)
3.60–3.51 (m, 1 H, CH2)
3.15 (d, J = 18.1 Hz, 1 H, CH2)
tive to those of the corresponding η5-coordinated indenyl pyridyl side chain functionalized indenes with Ru3(CO)12 in
complexes, especially for the benzo ring protons (from 7.77– refluxing xylene. The results clearly show the effects of the
6.34 to 6.49–3.35 ppm, see Table 2). This may be the result functionalized side chain on the reaction. The existence of
of the magnitude of back donation from the Ru atoms co- a bulky substituent on the indenyl ring may promote the
ordinated to the C6 or C5 ring. The η5:η2:η2 coordination formation of the syn-η5:η6-bonded indenyl clusters. The sol-
(5.96–3.35 ppm) shifts the resonances upfield relative to vent also has a significant effect on the reaction, and a
those observed for η5:η6-coordinated compounds (6.49– series of ionic clusters were obtained when heptane was
3.75 ppm).
used instead of xylene.
1
The H NMR spectrum of 18 shows 11 groups of peaks
for the pyridyl and benzo ring protons at 8.84–5.98 ppm
and 7 groups of peaks for the C5-ring H and CH2 protons
at 5.29–3.15 ppm, which is indicative of the unsymmetrical
structure. It is consistent with the X-ray diffraction analysis
results. Similar to that mentioned above, most of the chemi-
cal shifts of the corresponding protons in 18 are also shifted
upfield relative to those in 17.
Experimental Section
General Considerations: Schlenk and vacuum line techniques were
employed for all manipulations of air- and moisture-sensitive com-
pounds. All solvents were distilled from appropriate drying agents
1
under an atmosphere of argon before use. H NMR spectra were
recorded with a Bruker AV300 or VARIAN AS-400, and IR spectra
were recorded as KBr disks with a Nicolet 5DX FTIR spectrome-
ter. Mass spectra were obtained from a VG ZAB-HS. Elemental
analyses were performed with a Perkin–Elmer 240C analyzer. Li-
gand precursors 1,[9] 3,[21] and 6[17] were synthesized according to
literature procedures.
The 1H NMR spectra of the anions of compounds 19–24
are almost identical and show a singlet at about 16.4 ppm
(Table 3), which is consistent with the values reported ear-
lier.[20] One of the four H atoms [H(57A)] of the C5 ring of
the indenyl group in 22 (2.21–2.11 ppm) is shifted upfield
relative to the other three H atoms (3.24–3.02 ppm); this is
possibly due to the deshielding effect of the surrounding
groups (Figure 8). This phenomenon also appears in com-
pounds 20 and 23.
Ligand Precursor 2: The ligand precursor 2 was prepared following
the procedure as described for ligand precursor 1.[9] A solution of
6,6Ј-dimethylbenzofulvene (10.2 g, 65.4 mmol) in Et2O (50 mL)
was added to a solution prepared from 2,6-dimethylpyridine
(7.00 g, 65.4 mmol) in n-hexane (100 mL) and nBuLi (41.5 mL,
50.7 mmol). The mixture was stirred overnight at room temperature
and hydrolyzed with water. After separation and drying, the sol-
vents were removed under reduced pressure. The resulting oil was
distilled, and a yellow fraction at 140–143 °C/0.3 Torr was collected
Conclusion
A series of metal complexes with different bonding
modes of the indenyl ligand was prepared by reaction of (11.9 g, 69%). 1H NMR (300 MHz, CDCl3): δ = 7.78 (d, J =
1860
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Eur. J. Inorg. Chem. 2008, 1854–1864

Reactions of Pyridyl Side Chain Functionalized Indenes with Ru3(CO)12
1
Table 3. H NMR data of complexes 19–24 (in CDCl3, ppm).
[HRu6(CO)18]–
Pyridyl H, quinolyl H
or C6-ring H of indenyl
C5-ring H of indenyl
Other H
19 16.46 (s, 1 H)
8.14 (d, J = 5.4 Hz, 1 H)
8.06 (t, 1 H)
7.71 (d, J = 7.4 Hz, 1 H)
7.56 (d, J = 4.1 Hz, 2 H)
7.39–7.29 (m, 2 H)
7.18 (d, J = 8.7 Hz, 1 H)
8.51 (t, 1 H)
8.30 (d, J = 5.8 Hz, 1 H)
8.04 (d, J = 7.2 Hz, 1 H)
7.92
6.13 (d, J = 2.6 Hz, 1 H)
5.45 (d, J = 2.6 Hz, 1 H)
3.49 (d, J = 14.4 Hz, 1 H, Py-CH2)
3.08 (d, J = 14.4 Hz, 1 H, Py-CH2)
1.63 (d, J = 3.5 Hz, 6 H, Me)
20 16.41 (s, 1 H)
3.24–3.02 (m, 3 H)
2.21–2.11 (m, 1 H)
3.62 (d, J = 17.7 Hz, 1 H, Py-CH2)
3.46 (d, J = 17.7 Hz, 1 H, Py-CH2)
(t, 1 H) 7.59–7.48 (m, 2 H)
7.40 (m, 1 H)
1.34 (s, 3 H, Me), 1.09 (s, 3 H, Me)
7.02 (d, J = 7.6 Hz, 1 H)
7.90 (t, 1 H)
7.76 (d, J = 8.4 Hz, 1 H)
7.56 (m, 2 H)
7.42 (m, 2 H)
6.87 (d, J = 8.9 Hz, 1 H)
8.30 (t, 1 H)
21 16.47 (s, 1 H)
22 16.40 (s, 1 H)
6.41 (d, J = 2.8 Hz, 1 H)
5.53 (d, J = 2.8 Hz, 1 H)
3.44 (d, J = 14.3 Hz, 1 H, Py-CH2)
3.14 (d, J = 14.3 Hz, 1 H, Py-CH2)
1.97 (s, 3 H, Me), 1.77 (s, 3 H, Me)
1.53 (s, 3 H, Me)
3.24–3.03 (m, 3 H)
2.39–2.30 (m, 1 H)
3.57 (d, J = 17.3 Hz, 1 H, Py-CH2),
3.35 (d, J = 17.3 Hz, 1 H, Py-CH2)
2.23 (s, 3 H, Me), 1.26 (s, 3 H, Me)
1.09 (s, 3 H, Me)
7.81 (d, J = 7.5 Hz, 1 H)
7.61 (d, J = 7.5 Hz, 1 H),
7.50 (m, 2 H) 7.36 (t, 1 H)
7.11 (d, J = 8.3 Hz, 1 H)
8.91 (d, J = 8.3 Hz, 1 H)
8.26 (d, J = 8.2 Hz, 1 H)
23 16.38 (s, 1 H)
3.29 (t, 2 H)
3.12–3.02 (m, 1 H)
3.76 (d, J = 17.8 Hz, 1 H, Quin-CH2)
3.58 (d, J = 17.8 Hz, 1 H, Quin-CH2),
1.35 (s, 3 H, Me), 1.12 (s, 3 H, Me)
7.96 (d, J = 8.3 Hz, 1 H)
7.87 (t, 1 H), 7.74 (t, 1 H)
7.61–7.52 (m, 2 H)
2.68–2.56 (m, 1 H)
7.31–7.22 (m, 2 H)
6.90 (d, J = 7.7 Hz, 1 H)
9.33 (d, J = 5.3 Hz, 1 H)
8.14 (m, 1 H)
24 16.45 (s, 1 H)
5.23 (s, 1 H), 4.58 (d, J = 16.5 Hz, 1 H)
4.38 (d, J = 4.0 Hz, 1 H),
3.93–3.67 (m, 4 H)
7.87 (d, J = 7.9 Hz, 1 H)
3.38 (d, J = 21.7 Hz, 1 H),
3.20 (d, J = 21.7 Hz, 1 H)
(C5-ring H, Py-CH2 and Py-CH)
7.74–7.64 (m, 2 H)
7.55–7.44 (m, 2 H)
7.11 (t, 2 H)
6.98–6.90 (m, 2 H)
6.80 (d, J = 7.5 Hz, 1 H)
6.69–6.61 (m, 2 H),
6.54–6.48 (m, 1 H)
6.32 (d, J = 5.1 Hz, 1 H)
7.7 Hz, 1 H, Py-H), 7.49 (d, J = 7.3 Hz, 1 H, Py-H), 7.33 (t, J = at 130–133 °C/0.05 Torr was collected (5.33 g, 22%). 1H NMR
7.3 Hz, 1 H, Py-H), 7.22 (dd, J = 7.7 Hz, J = 6.5 Hz, 2 H, Ar-H), (300 MHz, CDCl3): δ = 7.78 (d, J = 7.6 Hz, 1 H, Ar-H), 7.49 (d,
6.89 (d, J = 7.6 Hz, 1 H, Ar-H), 6.44 (d, J = 7.7 Hz, 1 H, Ar-H),
J = 7.3 Hz, 1 H, Ar-H), 7.36–7.09 (m, 5 H, Ar-H), 6.93–6.87 (m,
6.06 (t, J = 2.1 Hz, 1 H, C5-ring H), 3.26 (br. s, 4 H, C5-ring H 2 H, Ar-H), 6.01 (t, J = 2.1 Hz, 1 H, C5-ring H), 3.25 (s, 2 H), 3.07
and Py-CH2), 2.51 (s, 3 H, Py-Me), 1.37 (s, 6 H, CMe2) ppm. 13C
NMR (75 MHz, CDCl3): δ = 158.9, 157.0, 151.6, 145.7, 144.0,
135.5, 128.3, 125.8, 124.1, 124.0, 122.2, 121.1, 120.4, 48.5, 37.6,
(s, 2 H, C5-ring H and Ar-CH2), 1.33 (s, 6 H, CMe2) ppm. 13C
NMR (75 MHz, CDCl3): δ = 151.3, 145.8, 144.1, 139.1, 130.4,
128.5, 127.5, 125.8, 125.7, 124.2, 124.1, 122.3, 46.6, 37.6, 37.3,
37.2, 27.4, 24.6 ppm. MS (ESI/CH2Cl2): m/z = 264 [M + H]+. 27.5 ppm. MS (EI): m/z = 248 [M]+. C19H20 (248.16): calcd. C
C19H21N (263.17): calcd. C 86.65, H 8.04, N 5.32; found C 86.50,
H 8.02, N 5.41.
91.88, H 8.12; found C 92.01, H 7.95.
Ligand Precursor 5: By using a similar procedure to that described
for 2, ligand precursor 5 was prepared from 2-methylquinoline,
nBuLi, and 6,6Ј-dimethylbenzofulvene in 98% yield as a yellow so-
Ligand Precursor 4: A solution of 6,6Ј-dimethylbenzofulvene
(15.6 g, 100 mmol) in THF (60 mL) was added to a solution of
PhCH2MgCl in THF, which was prepared from PhCH2Cl (12.7 g,
100 mmol) in THF (100 mL) and Mg (2.4 g, 100 mmol). The mix-
ture was heated at reflux for 12 h and then hydrolyzed with water.
After separation and drying, the solvents were removed under re-
duced pressure. The resulting oil was distilled, and a yellow fraction
1
lid. M.p. 94–95 °C. H NMR (400 MHz, CDCl3): δ = 8.09 (d, J =
8.4 Hz, 1 H), 7.87 (d, J = 7.7 Hz, 1 H), 7.80 (d, J = 8.5 Hz, 1 H),
7.71 (d, J = 8.2 Hz, 1 H), 7.67 (d, J = 8.1 Hz, 1 H), 7.53 (d, J =
7.4 Hz, 1 H), 7.47 (t, J = 7.5 Hz, 1 H), 7.38 (t, J = 7.5 Hz, 1 H),
7.26 (t, J = 7.4 Hz, 1 H), 6.74 (d, J = 8.5 Hz, 1 H, Quin and Ar-
Eur. J. Inorg. Chem. 2008, 1854–1864
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1861

D. Chen, S. Xu, H. Song, B. Wang
H), 6.04 (s, 1 H, C5-ring H), 3.50 (s, 2 H), 3.27 (s, 2 H, C5-ring H (KBr, νCO): ν = 1974 (s), 1931 (s), 1878 (m) cm–1. C H O Ru
4
FULL PAPER
˜
32 30
6
and Quin-CH2), 1.45 (s, 6 H, CMe2) ppm. 13C NMR (100 MHz, (917.82): calcd. C 42.01, H 3.31; found C 41.91, H 3.38.
CDCl3): δ = 160.3, 151.2, 147.7, 145.8, 143.9, 135.0, 129.2, 129.2,
128.6, 127.4, 126.7, 125.9, 125.7, 124.3, 122.7, 122.2, 49.3, 37.9,
37.3, 27.7 ppm. MS (ESI/CH2Cl2): m/z = 300 [M + H]+. C22H21N
(299.17): calcd. C 88.25, H 7.07, N 4.68; found C 88.21, H 7.10, N
4.65.
Reaction of 4 with Ru3(CO)12 in Xylene: By using a similar pro-
cedure to that described above, reaction of ligand precursor 4 with
Ru3(CO)12 gave red product 14 and orange product 13 in 8 and 9%
yield, respectively. Data for 13: M.p. 210 °C (dec.). IR (KBr, νCO):
ν = 1954 (s), 1781(s) cm–1. C H O Ru (810.09): calcd. C 62.36,
˜
42 38
4
2
H 4.74; found C 62.08, H 4.65. Data for 14: M.p. 210–212 °C (dec.).
IR (KBr, νCO): ν = 1968 (s), 1917 (s), 1880 (m) cm–1. C H O Ru
4
(1069.88): calcd. C 49.53, H 3.59; found C 49.49, H 3.46.
Reaction of 1 with Ru3(CO)12 in Xylene: A solution of Ru3(CO)12
(0.300 g, 0.469 mmol) and ligand precursor 1 (0.351 g, 1.41 mmol)
in xylene (30 mL) was heated at reflux for 5 h. The solvent was
removed under reduced pressure, and the residue was placed in an
Al2O3 column. Elution with CH2Cl2/petroleum ether developed
two bands. The first band gave 0.090 g (29%) of 8 as red crystals,
and the second band yielded 0.080 g (14%) of 7 as orange crystals.
˜
44 38
6
Reaction of 5 with Ru3(CO)12 in Xylene: By using a similar pro-
cedure to that described above, reaction of ligand precursor 5 with
Ru3(CO)12 gave red product 16 and orange product 15 in 16 and
10% yield, respectively. Data for 15: M.p. 215–216 °C. IR (KBr,
νCO): ν = 1946 (s), 1782 (s) cm–1. C H N O Ru (912.11): calcd.
Data for 7: M.p. 210–211 °C. IR (KBr, νCO): ν = 1957 (s), 1770 (s)
˜
˜
48 40
2
4
2
cm–1. C40H36N2O4Ru2 (812.08): calcd. C 59.25, H 4.47, N 3.45;
C 63.28, H 4.43, N 3.08; found C 63.48, H 4.64, N 3.19. Data for
found C 59.50, H 4.53, N 3.40. Data for 8: M.p. 135 °C (dec.). IR
16: M.p. 140–141 °C. IR (KBr, νCO): ν = 1965 (s), 1923 (s), 1871
˜
(m) cm–1. C50H40N2O6Ru4 (1171.91): calcd. C 51.37, H 3.45, N
2.40; found C 51.42, H 3.63, N 2.48.
(KBr, νCO): ν = 2034 (s), 1997 (s), 1977 (s), 1960 (s), 1952 (s), 1938
˜
(s), 1902 (s), 1851 (s) cm–1. C26H17NO8Ru4 (878.71): calcd. C 35.66,
H 1.96, N 1.60; found C 35.38, H 2.01, N 1.62.
Reaction of 6 with Ru3(CO)12 in Xylene: By using a similar pro-
cedure to that described above, reaction of ligand precursor 6 with
Ru3(CO)12 gave yellow product 18 and orange product 17 in 24 and
3% yield, respectively. Data for 17: M.p. 130–131 °C. IR (KBr,
Reaction of 2 with Ru3(CO)12 in Xylene: By using a similar pro-
cedure to that described above, reaction of ligand precursor 2 with
Ru3(CO)12 gave red product 10 and orange product 9 in 26 and
13% yield, respectively. Data for 9: M.p. 215–216 °C. IR (KBr,
νCO):
ν =
˜
1973 (s), 1936 (s), 1812 (m), 1774 (s) cm–1.
νCO): ν = 1957 (s), 1774 (s) cm–1. C H N O Ru (840.11): calcd.
˜
C34H24N2O4Ru2 (727.98): calcd. C 56.19, H 3.33, N 3.85; found C
42 40
2
4
2
C 59.99, H 4.80, N 3.33; found C 59.92, H 4.85, N 3.47. Data for
59.10, H 3.15, N 3.72. Data for 18: M.p. 180 °C (dec.). IR (KBr,
νCO): ν = 2000 (s), 1977 (s), 1924 (s), 1916 (s) cm–1. C H N O Ru
10: M.p. 170–171 °C. IR (KBr, νCO): ν = 1962 (s), 1918 (s), 1863
˜
˜
34 24
2
4
2
(s) cm–1. C44H40N2O6Ru4 (1099.91): calcd. C 8.00, H 3.67, N 2.55;
found C 48.11, H 3.62, N 2.48.
(727.98): calcd. C 56.19, H 3.33, N 3.85; found C 56.15, H 3.56, N
4.08.
Reaction of 3 with Ru3(CO)12 in Xylene: By using a similar pro-
cedure to that described above, reaction of ligand precursor 3 with
Ru3(CO)12 gave red product 12 and orange product 11 in 3 and
22% yield, respectively. Data for 11: M.p. 73–74 °C. IR (KBr, νCO):
Reaction of 1 with Ru3(CO)12 in Heptane: A solution of Ru3(CO)12
(0.300 g, 0.469 mmol) and 1 (0.117 g, 0.469 mmol) in heptane
(30 mL) was heated at reflux for 15 h. The solvent was removed
under reduced pressure, and the residue was placed in an Al2O3
column. Elution with CH2Cl2/petroleum ether gave products 8
ν = 1954 (s), 1778 (s) cm–1. C H O Ru (658.02): calcd. C 54.87,
˜
30 30
4
2
H 4.60; found C 55.10, H 4.85. Data for 12: M.p. 141–142 °C. IR (0.020 g), 19 (0.037 g), and 20 (0.11 g) in 5, 12, and 34% yield,
Table 4. Crystal data and summary of X-ray data collection for 8–10, 14, and 17.
8·CH2Cl2
9
10·CH2Cl2
14
17
Formula
Fw
T [K]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C53H36Cl2N2O16Ru8 C42H40N2O4Ru2
C23H22Cl2NO3Ru2
633.46
293(2)
C22H19O3Ru2
533.51
294(2)
monoclinic
P21/c
11.396(2)
8.4280(16)
19.785(4)
90
90.058(3)
90
1900.4(6)
4
1.865
1.609
C34H24N2O4Ru2
726.69
294(2)
orthorhombic
Pnma
15.803(4)
27.645(7)
6.5968(17)
90
1836.30
294(2)
838.90
293(2)
triclinic
triclinic
triclinic
¯
¯
¯
P1
P1
P1
10.363(6)
15.225(8)
18.276(11)
81.680(9)
81.218(9)
74.191(9)
2726(3)
6.579(3)
8.754(4)
16.552(7)
95.354(6)
99.032(6)
110.662(6)
869.5(6)
1
8.7574(15)
9.6907(17)
14.913(3)
79.430(3)
86.417(3)
70.619(2)
1173.7(4)
2
90
90
γ [°]
V [Å3]
2881.9(12)
4
1.675
1.090
1448
Z
2
Dcalcd. [gcm–3]
µ [mm–1]
F(000)
2.237
2.324
1.602
0.915
1.792
1.539
626
1764
426
1052
Crystal size [mm]
θ range [°]
No. of reflns collected
0.38ϫ0.34ϫ0.30
1.13–25.01
14344
0.30ϫ0.12ϫ0.12
1.26–26.14
4881
3403/0.0359
229
1.055
0.0503, 0.1294
0.0587, 0.1414
0.14ϫ0.10ϫ0.06
1.39–25.01
6151
4134/0.0233
283
1.107
0.0306, 0.0743
0.0449, 0.0931
0.40ϫ0.20ϫ0.12
1.79–26.29
10329
3857/0.0326
246
1.102
0.0285, 0.0694
0.0452, 0.0757
0.22ϫ0.20ϫ0.12
1.47–25.01
12992
2549/0.0694
196
1.183
0.0678, 0.1250
0.1114, 0.1549
No. of indep. reflns/Rint 9562/0.0170
No. of parameters
Goodness-of-fit on F2
R1, wR2 [IϾ2σ(I)]
R1, wR2 (all data)
734
1.077
0.0267, 0.0605
0.0379, 0.0667
1862
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Eur. J. Inorg. Chem. 2008, 1854–1864

Reactions of Pyridyl Side Chain Functionalized Indenes with Ru3(CO)12
Table 5. Crystal data and summary of X-ray data collection for 18, 21, 22, and 24.
18
21·CH2Cl2
22·CH2Cl2
24
Formula
Fw
C34H24N2O4Ru2
726.69
C39.50H22ClNO20Ru7
1573.52
C37.50H24ClNO18Ru6
1418.45
C49H26N2O19Ru7
1654.24
T [K]
294(2)
monoclinic
C2/c
15.2648(18)
15.9920(19)
24.900(3)
90
106.971(2)
90
293(2)
monoclinic
P21/c
10.0159(10)
14.3530(14)
33.460(3)
90
92.466(2)
90
294(2)
monoclinic
P21/n
24.314(3)
14.1785(17)
27.035(3)
90
104.731(2)
90
293(2)
Crystal system
Apace group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
triclinic
¯
P1
15.363(3)
19.088(3)
20.472(4)
95.687(4)
100.448(4)
113.147(3)
5331.4(17)
4
γ [°]
V [Å3]
5813.9(12)
8
1.660
4805.7(8)
4
2.175
9013.4(18)
8
2.091
Z
Dcalcd. [gcm–3]
2.060
2.004
µ [mm–1]
1.081
2.272
2.092
F(000)
2896
3004
5448
3172
Crystal size [mm]
θ range [°]
No. of reflns collected
No. of indep. reflns/Rint
No. of parameters
Goodness-of-fit on F2
R1, wR2 [IϾ2σ(I)]
R1, wR2 (all data)
0.28ϫ0.22ϫ0.20
1.71–26.38
16187
5940/0.0286
379
1.079
0.0286, 0.0623
0.0468, 0.0704
0.18ϫ0.12ϫ0.10
1.226–26.38
26818
9786/0.0648
634
0.988
0.0449, 0.0844
0.1062, 0.1043
0.32ϫ0.24ϫ0.20
1.01–26.40
50442
18356/0.0546
1148
1.011
0.0535, 0.1225
0.1065, 0.1491
0.22ϫ0.14ϫ0.04
1.03–25.02
27306
18707/0.0884
1522
1.019
0.0790, 0.1600
0.2398, 0.2404
respectively. Data for 19: M.p. 137 °C (dec.). IR (KBr, νCO): ν =
All calculations were performed by using the SHELXL-97 program
system. The crystal data and summary of X-ray data collection are
presented in Tables 4 and 5. CCDC-636913 (for 8), -636914 (for
9), -636915 (for 10), -655292 (for 14), -636916 (for 17), -636917 (for
18), -666253 (for 21), -666254 (for 22), and -666255 (for 24) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
˜
2050 (s), 2010 (s), 1954 (s) cm–1. C38H19NO20Ru7 (1522.38): calcd.
C 30.09, H 1.26, N 0.92; found C 30.57, H 1.74, N 1.11. Data for
20: M.p. 140–141 °C. IR (KBr, νCO): ν = 2012 (s), 1953 (s) cm–1.
˜
C36H21NO18Ru6 (1366.50): calcd. C 31.75, H 1.55, N 1.03; found
C 32.01, H 1.72, N 1.37.
Reaction of 2 with Ru3(CO)12 in Heptane: By using a similar pro-
cedure to that described above, reaction of 2 (0.370 g, 1.41 mmol)
with Ru3(CO)12 (0.300 g, 0.469 mmol) gave red products 21
(0.040 g) and 22 (0.080 g) in 13 and 25% yield, respectively. Data
Acknowledgments
for 21: M.p. 125 °C (dec.). IR (KBr, νCO): ν = 2056 (w), 2022 (s),
˜
1957 (w) cm–1. C39H21NO20Ru7 (1536.40): calcd. C 30.59, H 1.38,
We are grateful to the National Natural Science Foundation of
China (20672058, 20574036, 20421202), the Program for New Cen-
tury Excellent Talents in University (NCET-04–0229), and the Re-
search Fund for the Doctoral Program of Higher Education of
China (20070055020) for financial support.
N 0.91; found C 30.40, H 1.45, N 1.00. Data for 22: M.p. 118 °C
(dec.). IR (KBr, νCO): ν = 2054 (s), 2018 (s), 1998 (s), 1987 (m)
˜
cm–1. C37H23NO18Ru6 (1380.52): calcd. C 32.30, H 1.68, N 1.02;
found C 32.65, H 1.85, N 1.16.
Reaction of 5 with Ru3(CO)12 in Heptane: By using a similar pro-
cedure to that described above, reaction of 5 (0.421 g, 1.41 mmol)
with Ru3(CO)12 (0.300 g, 0.469 mmol) gave red product 23 (0.050 g)
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˜
2012 (s), 1954 (s) cm–1. C40H23NO18Ru6 (1416.52): calcd. C 34.02,
H 1.64, N 0.99; found C 33.78, H 1.92, N 1.03.
Reaction of 6 with Ru3(CO)12 in Heptane: By using a similar pro-
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with Ru3(CO)12 (0.300 g, 0.469 mmol) gave yellow product 18
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24: M.p. 130 °C (dec.). IR (KBr, νCO): ν = 2014 (s), 1952 (s) cm–1.
˜
C49H26N2O19Ru7 (1659.44): calcd. C 35.58, H 1.58, N 1.69; found
C 35.80, H 1.85, N 2.06.
Crystallographic Studies: Single crystals of complexes 8, 9, 10, 14,
17, 18, 21, 22, and 24 suitable for X-ray diffraction were obtained
from hexane/CH2Cl2 solutions. Data collection was performed with
a BRUKER SMART 1000 by using graphite-monochromated Mo-
Kα radiation (ω-2θ scans, λ = 0.71073 Å). Semiempirical absorption
corrections were applied for all complexes. The structures were
solved by direct methods and refined by full-matrix least-squares.
Eur. J. Inorg. Chem. 2008, 1854–1864
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1863

D. Chen, S. Xu, H. Song, B. Wang
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Received: November 6, 2007
Published Online: February 27, 2008
1864
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 1854–1864