Trinuclear and tetranuclear ruthenium carbonyl clusters derived from indenylphosphines: Cleavage of C-H and C-P bonds

Article abstract of DOI:10.1021/om200072g

Thermal treatment of Ru₃(CO)₁₂ with equimolar amounts of (1H-inden-3-yl)diphenylphosphine and (1H-inden-2-yl)diphenylphosphine in octane gave two isomeric trinuclear ruthenium clusters Ru₃(μ ₂-H)(μ₃-3-Ph₂PC₉H ₆)(CO)₉ (1) and Ru₃(μ₂-H) (μ₃-2-Ph₂PC₉H₆)(CO)₉ (2), respectively, via a C-H bond cleavage. Heating either 1 or 2 in octane afforded the trinuclear and tetranuclear ruthenium clusters Ru ₃(μ₃-PPh)(μ₃-C₉H ₆)(CO)₉ (3) and Ru₄(μ₄-PPh) (μ₄-C₉H₆)(CO)₁₁ (4) via double C-P bond cleavage. Thermal treatment of Ru₃(CO)₁₂ with (4,7-dimethyl-1H-inden-3-yl)diphenylphosphine in octane gave trinuclear ruthenium cluster Ru₃(μ₂-H)(μ₃-3-Ph ₂PC₁₁H₁₀)(CO)₉ (5) via a C-H bond cleavage. Heating 5 in octane afforded a trinuclear ruthenium cluster Ru ₃(μ₃-PPh)(μ₃-C₁₁H ₁₀)(CO)₉ (6) and two isomeric tetranuclear ruthenium clusters Ru₄(μ₃-PPh)(μ₂- η⁵:η¹-C₁₁H₁₀)(CO) ₁₁ (7) and [Ru₄(μ₄-PPh)(μ₄- C₁₁H₁₀)(CO)₁₁] (8) via double C-P bond cleavage. Thermal treatment of Ru₃(CO)₁₂ with (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine in toluene afforded two trinuclear ruthenium clusters Ru₃(μ₂-H) ₂(μ₃-3-Ph₂PC₁₂H ₁₁)(CO)₈ (9) via both sp³ and sp² C-H bond cleavage and Ru₃(μ₂-PPh₂) (μ₃-η²:η²:η⁵-C ₁₂H₁₃)(CO)₆ (10) via a C-P bond cleavage. Thermal treatment of Ru₃(CO)₁₂ with (3-methyl-1H-inden-1- yl)diphenylphosphine in toluene afforded a trinuclear ruthenium cluster Ru ₃(μ₂-H)(μ₃-3-Ph₂PC ₁₀H₈)(CO)₉] (11) via a C-H bond cleavage. The molecular structures of complexes 1-5 and 7-11 have been determined by single-crystal X-ray diffraction analysis.

Full text of DOI:10.1021/om200072g

ARTICLE
pubs.acs.org/Organometallics
Trinuclear and Tetranuclear Ruthenium Carbonyl Clusters Derived
from Indenylphosphines: Cleavage of CÀH and CÀP Bonds
Xing Tan,† Bin Li,† Shansheng Xu,† Haibin Song,† and Baiquan Wang*,†,‡
†State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China
‡State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, China
S Supporting Information
b
ABSTRACT: Thermal treatment of Ru3(CO)12 with equimo-
lar amounts of (1H-inden-3-yl)diphenylphosphine and (1H-
inden-2-yl)diphenylphosphine in octane gave two isomeric
trinuclear ruthenium clusters Ru3(μ2-H)(μ3-3-Ph2PC9H6)-
(CO)9 (1) and Ru3(μ2-H)(μ3-2-Ph2PC9H6)(CO)9 (2), re-
spectively, via a CÀH bond cleavage. Heating either 1 or 2 in
octane afforded the trinuclear and tetranuclear ruthenium clusters Ru3(μ3-PPh)(μ3-C9H6)(CO)9 (3) and Ru4(μ4-PPh)
(μ4-C9H6)(CO)11 (4) via double CÀP bond cleavage. Thermal treatment of Ru3(CO)12 with (4,7-dimethyl-1H-inden-3-
yl)diphenylphosphine in octane gave trinuclear ruthenium cluster Ru3(μ2-H)(μ3-3-Ph2PC11H10)(CO)9 (5) via a CÀH bond
cleavage. Heating 5 in octane afforded a trinuclear ruthenium cluster Ru3(μ3-PPh)(μ3-C11H10)(CO)9 (6) and two isomeric
tetranuclear ruthenium clusters Ru4(μ3-PPh)(μ2-η5:η1-C11H10)(CO)11 (7) and [Ru4(μ4-PPh)(μ4-C11H10)(CO)11] (8) via
double CÀP bond cleavage. Thermal treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine in toluene
afforded two trinuclear ruthenium clusters Ru3(μ2-H)2(μ3-3-Ph2PC12H11)(CO)8 (9) via both sp3 and sp2 CÀH bond cleavage and
Ru3(μ2-PPh2)(μ3-η2:η2:η5-C12H13)(CO)6 (10) via a CÀP bond cleavage. Thermal treatment of Ru3(CO)12 with (3-methyl-1H-
inden-1-yl)diphenylphosphine in toluene afforded a trinuclear ruthenium cluster Ru3(μ2-H)(μ3-3-Ph2PC10H8)(CO)9] (11) via a
CÀH bond cleavage. The molecular structures of complexes 1À5 and 7À11 have been determined by single-crystal X-ray
diffraction analysis.
’ INTRODUCTION
’ RESULTS AND DISCUSSION
The reactions of Ru3(CO)12 with phosphines have been ex-
tensively explored over the past several decades,1À5 and many
products derived from C(sp2)ÀH2,4 and CÀP3,4,5a bond clea-
vage have been isolated and structurally characterized. However,
there are rare examples of C(sp3)ÀH bond activation by ruthenium
clusters with assistance from coordinated phosphine atom.5 Indenyl
metal complexes have been widely studied due to their diverse and
flexible hapticities and the enhanced reactivities both in stoichio-
metric reactions and in catalysis in comparison to their cyclopenta-
dienyl analogues,6 which is referred to as the indenyl effect.7 Reac-
tions of indene derivatives with Ru3(CO)12 generally afforded the
η5-indenyl diruthenium carbonyl complexes,8 but in some cases
polynuclear ruthenium clusters with more complicated bonding
modes were obtained because of the flexible hapticities of indenyl
ligands.9 However, there are very few reports of indyne complexes of
metal clusters,10 so it is of interest to establish a convenient way to
synthesize them. Presented in this work are reactions of indenylpho-
sphines and their methyl-substituted derivatives with Ru3(CO)12,
leading to a series of trinulear and tetranuclear indyne ruthenium
carbonyl clusters and several other unexpected products, via CÀH
and CÀP bond cleavage. Especially, a novel trinuclear ruthenium
cluster was formed by methyl C(sp3)ÀH activation, which would be
described in detail.
Reactions of Ru3(CO)12 with (1H-Inden-3-yl)diphenylpho-
sphine and (1H-Inden-2-yl)diphenylphosphine. When Ru3-
(CO)12 reacted with equimolar amounts of (1H-inden-3-yl)dip-
henylphosphine and (1H-inden-2-yl)diphenylphosphine in re-
fluxing octane for 2 h, two isomeric trinuclear ruthenium clusters
Ru3(μ2-H)(μ3-3-Ph2PC9H6)(CO)9 (1) and Ru3(μ2-H)(μ3-2-
Ph2PC9H6)(CO)9 (2) were obtained in high yields, respectively
(Scheme 1). Simply substituted products Ru3(CO)12ÀnLn were
not detected because they may readily lose CO to allow metala-
tion at the indenyl rings, in preference to the phenyl rings. The
spectroscopic data of 1 and 2 are consistent with the proposed
structure. The IR spectra of 1 and 2 only show terminal carbonyl
1
absorptions at 2086À1960 cmÀ1. Their H NMR spectra show a
doublet for the bridging hydride (δ = À18.16 ppm for 1, À17.55
ppm for 2), while their 31P NMR spectra show only a singlet (δ =
35.7 ppm for 1, 35.4 ppm for 2). Single-crystal X-ray diffraction
analysis shows that 1and 2are isostructural clusters (Figures 1 and 2).
Both of them contain a μ3-Ph2PC9H6 unit, which is bonded to
one Ru atom through the coordination of the phosphorus atom,
Received: January 26, 2011
Published: March 23, 2011
r
2011 American Chemical Society
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Scheme 1
Figure 2. ORTEP view of the cluster Ru3(μ2-H)(μ3-2-Ph2PC9H6)-
(CO)9 (2) showing 30% ellipsoids. Hydrogen atoms except for the μ2-H
have been omitted for clarity. Selected bond lengths (Å): Ru(1)ÀRu(2)
2.742(1), Ru(1)ÀRu(3) 2.8535(9), Ru(2)ÀRu(3) 3.016(1), Ru(1)ÀC-
(10) 2.287(4), Ru(1)ÀC(11) 2.281(4), Ru(2)ÀC(11) 2.094(4), Ru-
(3)ÀP(1) 2.319(1), Ru(2)ÀH 1.79(5), Ru(3)ÀH 1.69(5), P(1)ÀC(10)
1.776(4), C(10)ÀC(11) 1.435(6).
Chart 1
Ru3(CO)12 in refluxing octane for 2 h, 3 could be converted into 4
in moderate yield. The IR spectrum of 4 shows terminal carbonyl
absorptions at 2084À1961 cmÀ1 and two bridging carbonyl absorp-
tions at 1867 and 1828 cmÀ1, while the IR spectrum of 3 only shows
terminal carbonyl absorptions at 2087À1970 cmÀ1. The 31P NMR
spectra of 3 and 4 show only one singlet at δ = 388.7 (for 3) and δ =
262.7 (for 4) ppm, indicating the occurrence of CÀP bond cleavage.
Clusters 3 and 4 gave similar but different 1H NMR signals, which
show the presence of only 11 protons with a singlet at δ = 4.10 (for
3) and δ = 2.94 (for 4) ppm assigned to the CH2 group.
The structures of clusters 3 and 4 were finally confirmed by
single-crystal X-ray diffraction studies (Figures 3 and 4). Cluster 3
consists of an open triangular cluster of Ru atoms, each of
which is coordinated by three carbonyl groups. The plane of the
three Ru atoms is coordinated on one side by a μ3-PPh ligand and
on the opposite side by a μ3-indyne ligand. The RuÀRu bond
lengths [Ru(1)ÀRu(2) = 2.8355(8) Å and Ru(2)ÀRu(3) =
2.8089(7) Å] are consistent with normal RuÀRu bonding.
The μ3-indyne ligand is bound to the Ru3 chain through two σ
CÀRu bonds and an η2-interaction between C(10), C(11), and
Ru(2). This structure is closely related to the known structure of
Os3(CO)9(μ2-H)2(μ3-C9H6) (Chart 2), which is formed by
reaction of indene with Os3(CO)12.10a
Figure 1. ORTEP view of the cluster Ru3(μ2-H)(μ3-3-Ph2PC9H6)-
(CO)9 (1) showing 30% ellipsoids. Hydrogen atoms except for the μ2-
H have been omitted for clarity. Selected bond lengths (Å): Ru(1)ÀRu-
(2) 3.0135(5), Ru(1)ÀRu(3) 2.7472(5), Ru(2)ÀRu(3) 2.8453(4), Ru-
(1)ÀC(30) 2.066(3), Ru(2)ÀP(1) 2.3422(8), Ru(3)ÀC(22) 2.362(3),
Ru(3)ÀC(30) 2.241(3), Ru(1)ÀH 1.70(5), Ru(2)ÀH 1.86(5), P(1)À
C(22) 1.791(3), C(22)ÀC(30) 1.430(4).
to another Ru atom through a σ RuÀC bond, and to the third Ru
atom in an η2 mode. The structures of 1 and 2 are similar to those of
related [Os3(μ2-H)(μ3-RPhPC6H4)(CO)9] (R = Me or Ph)
(Chart 1) complexes.11
Heating either 1 or 2 in octane or toluene for 7 h resulted in
the formation of two products: trinuclear ruthenium cluster Ru3
(μ3-PPh)(μ3-C9H6)(CO)9 (3) and tetranuclear ruthenium cluster
Ru4(μ4-PPh)(μ4-C9H6)(CO)11 (4). By reaction with 1 equiv of
In molecule 4, a square Ru4 unit is capped on one side,
approximately symmetrically, by a μ4-PPh ligand. The μ4-indyne
ligand is capped on the other side as a four-electron donor. The
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Chart 2
Chart 3
Figure 3. ORTEP view of the cluster Ru3(μ3-PPh)(μ3-C9H6)
(CO)9 (3) showing 30% ellipsoids. Hydrogen atoms have been omitted
for clarity. Selected bond lengths (Å): Ru(1)ÀRu(2) 2.8355(8), Ru-
(2)ÀRu(3) 2.8089(7), Ru(1)ÀC(10) 2.092(4), Ru(1)ÀP(1) 2.294(1),
Ru(2)ÀC(10) 2.311(4), Ru(2)ÀC(11) 2.374(4), Ru(2)ÀP(1) 2.429(1),
Ru(3)ÀC(11) 2.099(4), Ru(3)ÀP(1) 2.296(1), C(10)ÀC(11) 1.419(5).
with Os3(CO)12, with a similar “butterfly”arrangement of four metal
atoms.10b
Synthesis and Characterization of Clusters 5À8. Treat-
ment of Ru3(CO)12 with an equimolar amount of (4,7-dimethyl-
1H-inden-3-yl)diphenylphosphine in refluxing octane for 30 min
afforded a complex Ru3(μ2-H)(μ3-3-Ph2PC9H4Me2)(CO)9 (5)
in high yield. The structure of 5 is confirmed by single-crystal
X-ray diffraction studies with two independent molecules 5a and
5b cocrystallized in the asymmetric unit (Figure 5). Although the
basic shapes of molecules 5a and 5b are the same, the RuÀRu
bond lengths of them have a significant difference. In molecule
5b, the bond length of Ru(1)ÀRu(2) is 2.8245(4) Å, much sh-
orter than the corresponding RuÀRu bond length of 5a
[Ru(6)ÀRu(5) = 3.0055(5) Å]. On the contrary, the bond
length of Ru(2)ÀRu(3) of 5b is 2.9838 (4) Å, much longer than
the corresponding RuÀRu bond length of 5a [Ru(5)ÀRu(4) =
2.8311(5) Å]. The most obvious difference between 5a and 5b is
the position of the bridging hydride, which is located and refined
crystallographically. Similar to cluster 1, the hydride of 5a is
attached to Ru(6) and Ru(5) atoms. However, instead of being
attached to the corresponding Ru(1) and Ru(2) atoms, the
hydride of 5b is connected to Ru(3) and Ru(2) atoms. Thus, the
hydride is connected to the longest RuÀRu edge of each
[Ru(6)ÀRu(5) for 5a, Ru(2)ÀRu(3) for 5b]. Although two
Figure 4. ORTEP view of the cluster Ru4(μ4-PPh)(μ4-C9H6)(CO)11
(4) showing 30% ellipsoids. Hydrogen atoms have been omitted for
clarity. Selected bond lengths (Å): Ru(1)ÀRu(2) 2.752(1), Ru(1)ÀRu-
(4) 2.885(1), Ru(2)ÀRu(3) 2.745(1), Ru(3)ÀRu(4) 2.829(1), Ru-
(1)ÀP(1) 2.442(1), Ru(1)ÀC(12) 2.403(3), Ru(1)ÀC(13) 2.317(3),
Ru(2)ÀP(1) 2.407(1), Ru(2)ÀC(13) 2.145(3), Ru(3)ÀP(1) 2.426(1),
Ru(3)ÀC(12) 2.436(3), Ru(3)ÀC(13) 2.328(3), Ru(4)ÀP(1) 2.362(1),
Ru(4)ÀC(12) 2.102(3), C(12)ÀC(13) 1.438(4).
1
different hydrides appear in the solid state, the H NMR spec-
trum of 5 in CDCl3 solution shows only a broad singlet at δ =
À17.58 ppm for the hydride, while the hydride in both 1 and 2
shows a doublet at δ = À18.16 and À17.55 ppm, respectively.
These results suggest that molecules 5a and 5b can be trans-
formed each to the other rapidly in solution at room temperature.
Its IR spectrum shows only terminal carbonyl absorptions at
2084À1967 cmÀ1, and its 31P NMR spectrum shows a singlet at
δ = 35.2 ppm.
Heating 5 in refluxing octane for 2 h afforded a trinuclear
ruthenium cluster Ru3(μ3-PPh)(μ3-C11H10)(CO)9 (6) and two
isomeric tetranuclear ruthenium clusters Ru4(μ3-PPh)(μ2-η5:η1-
C11H10)(CO)11 (7) and Ru4(μ4-PPh)(μ4-C11H10)(CO)11 (8)
(Scheme 2). However, heating 5 in toluene only afforded cluster 8
in low yield. Because of the close analogy in structures between
ndyne plane is almost perpendicular to the Ru4 plane (the dihedral
angle is 91.0°), and the coordinated CÀC bond is diagonally
disposed across the Ru4 square. There are two bridging carbonyl
ligands along the shorter RuÀRu edges [Ru(1)ÀRu(2) and
Ru(2)ÀRu(3)] and nine terminal carbonyl ligands, which is con-
sistent with its IR spectrum. This geometry bears closest resem-
blance to that of known Ru4(μ4-PR)(μ4-X)(CO)11, where X =
alkyne,12 thiophyne,4j and pyrrolyne.4k Lewis and co-workers re-
ported a tetranuclear osmium indyne cluster Os4(μ4-C9H6)(CO)12
(Chart 3), which is the minor product of the reaction of indene
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ARTICLE
triangle plane is 32.7°. There are four RuÀRu bonds, with two normal
lengths [Ru(1)ÀRu(3) = 2.8644(3) Å, Ru(2)ÀRu(3) = 2.8082(3)
Å] and two elongated lengths [Ru(1)ÀRu(2) = 2.9181(3) Å,
Ru(2)ÀRu(4) =2.9293(3) Å]. Aμ3-PPh ligand is attached to Ru(2),
Ru(3), and Ru(4). There are 11 carbonyl ligands, three of which bond
to Ru(2), Ru(3), and Ru(4), respectively, two to Ru(1). The
C(2)ÀO(2) carbonyl ligand is found to be semibridging the Ru-
(1)ÀRu(3) edge [Ru(1)ÀC(2) = 1.882(2) Å, Ru(3)ÀC(2) =
2.951(2) Å, Ru(1)ÀC(2)ÀO(2) = 169.8(2)°], and the rest are
considered as terminal carbonyls. The indenyl ligand donates a total of
6 electrons, so this cluster has a total of 64 cluster valence electrons
(CVE), which is consistent with 8 skeletal electron pair (SEP) count
for an arachno polyhedron from a PSEPT13 viewpoint. The spectro-
scopic data of 7 are consistent with the proposed structure. Its IR
spectrum shows carbonyl absorptions at 2082À1943 cmÀ1, while its
1H NMR spectrum shows one doublet at δ = 5.10 ppm and one
singlet at δ = 4.76 ppm for the two protons on the Cp ring. Its 31P
NMR spectrum shows a singlet at δ = 432.3 ppm, which is consistent
with the presence of a μ3-phosphido ligand.
In our previous experiment, thermolysis of cluster 1 or 2 in
octane afforded the trinuclear indyne cluster 3 as the major
product, and only a small amount of tetranuclear indyne cluster 4
was obtained (see Experimental Section). Differently, thermo-
lysis of cluster 5 afforded the tetranuclear indyne cluster 8 as
the major product, and the trinuclear indyne cluster 6 and the
η5:η1-indenyl tetranuclear cluster 7 as minor products. Addition-
ally, further experiment supports that cluster 4 was formed from
cluster 3. Thus, we postulate that cluster 6could be readily converted
to cluster 8. Unfortunately, further conversion of cluster 6 was not
carried out due to the poor yield of cluster 6. It is noteworthy that the
formation of cluster 7 should involve a [1,3]-H shift on the five-
member ring, but the real mechanism is unknown at present.
Synthesis and Characterization of Clusters 9À11. Thermal
treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-inden-1-yl)
diphenylphosphine or (3-methyl-1H-inden-1-yl) diphenylpho-
sphine in octane for 4 h afforded only several minor unidentified
products. When we changed the solvent to toluene, several
products were isolated and characterized. However, the yields
of these products are relatively low, with the formation of a large
amount of dark solid that was not soluble in common organic
solvents. The steric hindrance of the 3-position methyl group of
these ligands may discourage the cyclometalation of their simply
substituted products [Ru3(CO)12ÀnLn], which may have poor
thermal stability and readily decompose to the unidentified
dark solid.
Treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-inden-1-
yl)diphenylphosphine in refluxing toluene for 4 h gave two
major products, Ru3(μ2-H)2(μ3-3-Ph2PC12H11)(CO)8 (9) and
Ru3(μ2-PPh2)(μ3-η2:η2:η5-C12H13)(CO)6 (10), in low yield
(Scheme 3). The structures of clusters 9 and 10 were confirmed
by single-crystal X-ray diffraction studies (Figures 7 and 8).
Cluster 9 consists of a closed triangular cluster of Ru atoms
capped on side face by an indenyl moiety (C12H11), which is
attached to a phosphine atom coordinated to Ru(2). There are
three RuÀRu bond interaction, with two normal lengths
[Ru(1)ÀRu(2) = 2.8664(6) Å, Ru(1)ÀRu(3) = 2.8461(6) Å]
and one elongated length [Ru(2)ÀRu(3) = 2.9828(6) Å]. There
are eight terminal carbonyls, three of which are bonded to Ru(1)
and Ru(2), respectively, two to Ru(3), and two bridging hydrides
(located and refined crystallographically). It is noteworthy that
the methylene carbon C(9) is bonded with Ru(3) through
an intramolecular sp3 CÀH bond activation. The lengths of
Figure 5. ORTEP view of the cluster Ru3(μ2-H)(μ3-3-Ph2PC9
H4Me2)(CO)9 (5) showing 30% ellipsoids. There are two independent
molecules 5a (top) and 5b (bottom) in the unit cell. Hydrogen atoms
except for the μ2-H have been omitted for clarity. Selected bond lengths
(Å): Ru(1)ÀRu(2) 2.8245(4), Ru(1)ÀRu(3) 2.7542(5), Ru(2)ÀRu-
(3) 2.9838(5), Ru(1)ÀC(11) 2.070(3), Ru(2)ÀP(1) 2.3487(8), Ru-
(2)ÀH(1) 1.60(4), Ru(3)ÀC(10) 2.338(3), Ru(3)ÀC(11) 2.291(3),
Ru(3)ÀH(1) 1.99(4), P(1)ÀC(10) 1.803(3), C(10)ÀC(11) 1.428(4),
Ru(4)ÀRu(5) 2.8311(5), Ru(4)ÀRu(6) 2.7513(4), Ru(5)ÀRu(6)
3.0055(5), Ru(4)ÀC(42) 2.289(3), Ru(4)ÀC(43) 2.244(3), Ru-
(5)ÀP(2) 2.3498(8), Ru(5)ÀH(2) 1.71(3), Ru(6)ÀC(43) 2.070(3),
Ru(6)ÀH(2) 1.72(3), P(2)ÀC(42) 1.790(3), C(42)ÀC(43) 1.444(4).
clusters 3 and 6, and that between the clusters 4 and 8, the features of
clusters 6 and 8 will not be described in detail.
The structure of cluster 7 was confirmed by single-crystal
X-ray diffraction studies (Figure 6). Cluster 7 consists of a
tetranuclear metal core exhibiting an open tetrahedral geometry.
The top atom Ru(4) is bonded to the Cp ring through a σ CÀRu
bond [Ru(4)ÀC(13) = 2.093(2) Å]. The other three Ru atoms
[Ru(1), Ru(2), Ru(3)] compose a closed triangle, with Ru(1)
bonded to the indenyl group through an η5 interaction. The
lengths of five RuÀC(Cp) bonds are significant different, ranging
from 2.188(2) Å [Ru(1)ÀC(14)] to 2.311(2) Å [Ru(1)ÀC(16)].
The dihedral angle between the indenyl plane and the closed Ru3
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Scheme 2
Scheme 3
Cluster 10 (Figure 9) consists of a closed triangular cluster of
Ru atoms with the μ3-indenyl ligand (C12H13) lying over on one
side of the triangular in an η5:η2:η2 mode. On the other side,
Ru(1) and Ru(2) are capped by a μ2-PPh2 ligand. There are six
terminal carbonyls, two of which are bonded to one Ru atom.
The spectroscopic data of 10 are consistent with the proposed
structure. The IR spectrum of 10 only shows terminal carbonyl
absorptions at 2011À1914 cmÀ1. In the 1H NMR spectrum, the
signals of four protons on the indenyl ring are present as four
doublets at δ = 5.29, 4.96, 4.52, and 4.39 ppm. The 31P NMR
spectrum shows a singlet at δ = 216.5 ppm, which is consistent
with the presence of a μ2-phosphido ligand. A few indenyl
ruthenium complexes with η5:η2:η2 coordination mode have
been reported, which are obtained by heating indene derivatives
with Ru3(CO)12.9a,c,d,f No indyne product was isolated by
thermal treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-in-
den-1-yl)diphenylphosphine. Thus, we propose the 3-position
methyl group of this ligand plays a significant role in the
formation of η5:η2:η2-indenyl cluster 10 by suppressing the
formation indyne clusters.
Figure 6. ORTEP view of the cluster Ru4(μ3-PPh)(μ2-η5:η1-
C9H4Me2)(CO)11 (7) showing 30% ellipsoids. Hydrogen atoms have been
omitted for clarity. Selected bond lengths (Å): Ru(1)ÀRu(2) 2.9181(3),
Ru(1)ÀRu(3) 2.8644(3), Ru(2)ÀRu(3) 2.8082(3), Ru(2)ÀRu(4)
2.9293(3), Ru(1)ÀC(12) 2.246(2), Ru(1)ÀC(13) 2.256(2), Ru(1)ÀC-
(14) 2.188(2), Ru(1)ÀC(15) 2.257(2), Ru(1)ÀC(16) 2.311(2), Ru-
(2)ÀP(1) 2.3589(5), Ru(3)ÀP(1) 2.3133(5), Ru(4)ÀP(1) 2.3150(5),
Ru(4)ÀC(13) 2.093(2).
C(9)ÀC(10) [1.449(3) Å] and C(10)ÀC(11) [1.410(3) Å] are
similar, and the lengths of Ru(3)ÀC(9) [2.172(3) Å], Ru-
(3)ÀC(10) [2.271(2) Å], and Ru(3)ÀC(11) [2.286(2) Å] are
consistent with normal RuÀC(sp2) bonding, strongly support-
ing an η3 coordination mode between C(9), C(10), C(11), and
Ru(3). The spectroscopic data for cluster 9 are in good agreement
with the X-ray data. Its IR spectrum only shows terminal carbonyl
The examples of methyl CÀH bond activations promoted by
ruthenium clusters are still scarce,5b,9g,14 in most of which the act-
ivated methyl group is attached to an aza-heterocycle (e.g., NHC,
pyrrole, or pyridine). In these cases, the driving force of the CÀH
activation process is contributed to the chelating ability of the
aza-heterocycle ligand, which induces the interaction of a methyl
group with the metal atoms.
1
absorptions at 2078À1948 cmÀ1. In its H NMR spectrum, the
signals of the hydrides are present as a doublet at δ = À14.41
ppm and a singlet at δ = À16.30 ppm. Its 31P{1H} NMR spectrum
shows a singlet at δ = 15.5 ppm, which is significantly shifted to
lower frequency in comparison with the clusters 1, 2, and 5 (δ =
35.2À35.7 ppm).
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ARTICLE
Figure 9. ORTEP view of the cluster [Ru3(μ2-PPh2)(μ3-η2:η2:η5-
C12H13)(CO)6] (10) showing 30% ellipsoids. Hydrogen atoms have been
omitted for clarity. Selected bond lengths (Å): Ru(1)ÀRu(2) 2.7483(7),
Ru(1)ÀRu(3) 2.9180(9), Ru(2)ÀRu(3) 2.9263(7), Ru(1)ÀP(1)
2.315(1), Ru(1)ÀC(20) 2.346(3), Ru(1)ÀC(21) 2.337(3), Ru(2)ÀP(1)
2.311(1), Ru(2)ÀC(22) 2.357(3), Ru(2)ÀC(23) 2.264(3), Ru(3)ÀC-
(24) 2.241(3), Ru(3)ÀC(25) 2.263(3), Ru(3)ÀC(26) 2.238(3), Ru-
(3)ÀC(27) 2.214(3), Ru(3)ÀC(28) 2.202(3), C(20)ÀC(21) 1.387(4),
C(22)ÀC(23) 1.421(4).
Figure 7. ORTEP view of the cluster Ru4(μ4-PPh)2(μ4-C9H4Me2)(CO)11
(8) showing 30% ellipsoids. Hydrogen atoms have been omitted for
clarity. Selected bond lengths (Å): Ru(1)ÀRu(2) 2.7539(4), Ru(1)ÀRu(4)
2.8312(4), Ru(2)ÀRu(3) 2.7470(4), Ru(3)ÀRu(4) 2.8440(4), Ru(1)ÀP-
(1) 2.4155(7), Ru(1)ÀC(12) 2.434(2), Ru(1)ÀC(13) 2.356(2), Ru-
(2)ÀP(1) 2.3858(7), Ru(2)ÀC(13) 2.167(2), Ru(3)ÀP(1) 2.4110(7),
Ru(3)ÀC(12) 2.522(2),Ru(3)ÀC(13) 2.315(2),Ru(4)ÀP(1) 2.3581(7),
Ru(4)ÀC(12) 2.137(2), C(12)ÀC(13) 1.417(3).
Figure 10. ORTEP view of the cluster [Ru3(μ2-H)(μ3-η1:η2-3-
Ph2PC9H5Me)(CO)9] (11) showing 30% ellipsoids. Hydrogen atoms
except for the μ2-H have been omitted for clarity. Selected bond lengths
(Å): Ru(1)ÀRu(2) 3.015(1), Ru(1)ÀRu(3) 2.745(1), Ru(2)ÀRu(3)
2.855(1), Ru(1)ÀC(18) 2.078(7), Ru(1)ÀH 1.70(1), Ru(2)ÀP(1)
2.338(2), Ru(2)ÀH 1.70(1), Ru(3)ÀC(10) 2.360(6), Ru(3)ÀC(18)
2.239(6), P(1)ÀC(10) 1.798(6), C(10)ÀC(18) 1.433(9).
Figure 8. ORTEP view of the cluster Ru3(μ2-H)2(μ3-3-Ph2PC12H11)-
(CO)8] (9) showing 30% ellipsoids. Hydrogen atoms except for the two
μ2-H have been omitted for clarity. Selected bond lengths (Å): Ru(1)ÀRu-
(2) 2.8664(6), Ru(1)ÀRu(3) 2.8461(6), Ru(2)ÀRu(3) 2.9828(6), Ru-
(1)ÀC(11) 2.101(2), Ru(1)ÀH(1) 1.77(2), Ru(2)ÀP(1) 2.3869(8),
Ru(2)ÀH(2) 1.70(2), Ru(3)ÀC(9) 2.172(3), Ru(3)ÀC(10) 2.271(2),
Ru(3)ÀC(11) 2.286(2), Ru(3)ÀH(1) 1.77(3), Ru(3)ÀH(2) 1.83(3),
P(1)ÀC(12) 1.856(3), C(9)ÀC(10) 1.449(3), C(10)ÀC(11) 1.410(3),
C(11)ÀC(12) 1.528(3).
(CO)9 (11, Figure 10) was isolated, which had a structure similar
to cluster 1 (Scheme 4). According to these results, the 7-posi-
tion methyl group of (3,4,7-trimethyl-1H-inden-1-yl)diphe-
nylphosphine ligand seems essential to the C(sp3)ÀH bond
activation. We postulate that the steric hindrance of 7-position
methyl makes the triruthenium cluster core very close to the
3-position methyl group, thereby enabling oxidative addition of
CÀH bonds to the ruthenium center.
To understand the process of C(sp3)ÀH bond activation in
the formation of cluster 9, we further studied the reaction of
Ru3(CO)12 with (3-methyl-1H-inden-1-yl)diphenylphosphine.
However, no C(sp3)ÀH bond activated product was obtained.
Instead, a cyclometalation cluster Ru3(μ2-H)(μ3-3-Ph2PC10H8)
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for 2 h gave complex 2 (145 mg, 72%) as an orange solid. Mp 160À161 °C
(dec). Anal. CalcdforC30H17O9PRu3: C, 42.11; H, 2.00. Found: C, 42.43; H,
2.14. 1HNMR(CDCl3):δ7.91 (br s, 2H, ArÀH), 7.86 (s, 1H, ArÀH), 7.56
(s, 3H, ArÀH), 7.28 (br s, 8H, ArÀH), 3.75 (m, 2H, CH2), À17.55 (d, J =
18.6 Hz, 1H, μ2-H) ppm. 31P{1H} NMR (CDCl3): δ 35.4 (s) ppm. IR
(νCO, cmÀ1): 2086 (s), 2054 (s), 2029 (s), 1998 (s), 1968 (s).
Thermolysis of Complex 1. A solution of 1 (165 mg, 0.193
mmol) in octane (30 mL) was refluxed for 7 h to give a dark brown
solution. After removal of solvent in vacuo, the residue was chromato-
graphed on silica with petroleum ether/CH2Cl2 (15/1) as eluent. The
first band gave complex 3 (58 mg, 39%) as a yellow solid. From the
second band, unreacted 1 (69 mg, 42%) was recovered. The third band
afforded complex 4 (6 mg, 4%) as a red solid.
Complex 3. Mp 155À156 °C (dec). Anal. Calcd for C24H11O9PRu3:
C, 37.07; H, 1.43. Found: C, 37.18; H, 1.63. 1H NMR (CDCl3): δ 8.00
(d, J = 6.1 Hz, 1H, ArÀH), 7.58 (m, 2H, ArÀH), 7.41 (s, 3H, ArÀH),
7.30 (m, 3H, ArÀH), 4.10 (s, 2H, CH2) ppm. 31P{1H} NMR (CDCl3):
δ 388.7 (s) ppm. IR (νCO, cmÀ1): 2087 (m), 2062 (s), 2049 (s), 2003 (s),
1970 (s).
Complex 4. Mp 175À176 °C (dec). Anal. Calcd for C26H11O11PRu4:
C, 33.41; H, 1.19. Found: C, 33.25; H, 1.31. 1H NMR (CDCl3): δ 8.10
(d, J = 7.4 Hz, 1H, ArÀH), 7.25À7.17 (m, 5H, ArÀH), 6.90 (d, J = 7.1
Hz, 1H, ArÀH), 6.59 (dd, J = 7.2, 14.5 Hz, 2H, ArÀH), 2.94 (s, 2H,
CH2) ppm. 31P{1H} NMR (CDCl3): δ 262.7 (s) ppm. IR (νCO, cmÀ1):
2084 (s), 2030 (s), 1993 (s), 1961 (s), 1867 (m), 1828 (s).
Thermolysis of Complex 2. Using a procedure similar to that
described for the thermolysis of 1, thermolysis of 2 in refluxing octane
gave complex 3 (45 mg, 43%), unreacted 2 (30 mg, 26%), and complex 4
(4 mg, 4%).
Reaction of Ru3(CO)12 with Complex 3. A solution of Ru3-
(CO)12 (87 mg, 0.136 mmol) and 3 (106 mg, 0.136 mmol) in octane
(20 mL) was refluxed for 2 h to give a dark brown solution (TLC rev-
ealed no presence of 3). After removal of solvent in vacuo, the residue
was chromatographed on silica with petroleum ether/CH2Cl2 (15/1) as
eluent to give two bands. From the first band, 29 mg (33%) of unreacted
Ru3(CO)12 was recovered. The second band afforded 52 mg (41%) of 4.
Reaction of Ru3(CO)12 with (4,7-Dimethyl-1H-inden-3-
yl)diphenylphosphine. Using a procedure similar to that described
for the synthesis of 1, reaction of Ru3(CO)12 (150 mg, 0.235 mmol) and
(4,7-dimethyl-1H-inden-3-yl)diphenylphosphine (78 mg, 0.236 mmol)
in refluxing octane (30 mL) for 30 min gave 183 mg (88%) of complex 5
as an orange solid. Mp 159À160 °C (dec). Anal. Calcd for C32H21O9-
PRu3: C, 43.49; H, 2.40. Found: C, 43.54; H, 2.37. 1H NMR (CDCl3): δ
7.48À7.21 (m, 8H, ArÀH), 7.02 (br s, 2H, ArÀH), 6.84 (d, J = 7.7 Hz,
1H, ArÀH), 6.73 (d, J = 7.6 Hz, 1H, ArÀH), 4.30 (s, 2H, CH2), 2.31 (s,
3H, CH3), 1.33 (s, 3H, CH3), À17.58 (s, 1H, μ2-H) ppm. 31P{1H}
NMR (CDCl3): δ 35.2 (s) ppm. IR (νCO, cmÀ1): 2084 (s), 2054 (s),
2028 (s), 1992 (s), 1967 (s).
Thermolysis of Complex 5. A solution of 5 (127 mg, 0.144
mmol) in octane (30 mL) was refluxed for 2 h to give a dark brown
solution. After removal of solvent in vacuo, the residue was chromato-
graphed on silica with petroleum ether as eluent. The first band gave a
mixture of complexes 6 and 7 as a red oil. Further purification of the
mixture by recrystallization with hexane gave 10 mg (9%) of 6 as a yellow
solid and 4 mg (4%) of 7 as a red solid. From the second band, 46 mg
(36%) of unreacted 5 was recovered. The third band afforded 23 mg
(22%) of complex 8 as a red-brown solid.
Scheme 4
In summary, we have studied the reactions of a series of
indenylphosphines derivatives with Ru3(CO)12, and trinuclear
and tetranuclear ruthenium clusters 1À11 were obtained via
CÀH bond and CÀP bond cleavage. The position of methyl
substituents on the indenyl ring strongly affects the mode of
CÀH and CÀP bond cleavage, but the real mechanism of the
formation of these clusters is not very clear. Thermolysis of the
cyclometalation clusters 1, 2, and 5 could easily prepare a series
of trinuclear and tetranuclear indyne products 3, 4, 6, and 8, via
CÀP bond cleavage. The unexpected η5:η1-indenyl tetranuclear
ruthenium cluster 7 and η5:η2:η2-indenyl trinuclear ruthenium
cluster 10 were formed via CÀP bond cleavage as well. The
formation of cluster 9 involves intramolecular methyl C(sp3)ÀH
bond activation, which represents a rare example of C(sp3)ÀH
bond activation by ruthenium clusters with assistance from
coordinated phosphine atom. These results may help us gain
more insights into the reactivities of indenylphosphine deriva-
tives toward ruthenium complexes and promote their application
in catalysis.
’ EXPERIMENTAL SECTION
General Considerations. Schlenk- and vacuum-line techniques
were employed for all manipulations. All solvents were distilled from
appropriate drying agents under argon before use. H and 31P NMR
1
spectra were recorded on a Bruker AV400 spectrometer. IR spectra were
recorded as KBr disks on a Nicolet 380 FT-IR spectrometer. Elemental
analyses were performed on a Perkin-Elmer 240C analyzer by Prof.
Jianxin Ma of the state key laboratory. (1H-Inden-3-yl)diphenylphosphine,15
(1H-inden-2-yl)diphenylphosphine,16 (4,7-dimethyl-1H-inden-3-yl)diphe-
nylphosphine,17 (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine,17 and
(3-methyl-1H-inden-1-yl)diphenylphosphine17 were prepared according to
the literature procedures.
Reaction of Ru3(CO)12 with (1H-Inden-3-yl)diphenylpho-
sphine. A solution of Ru3(CO)12 (150 mg, 0.235 mmol) and (1H-
inden-3-yl)diphenylphosphine (71 mg, 0.236 mmol) in octane (30 mL)
was refluxed for 2 h to give a dark orange solution. After removal of
solvent in vacuo, the residue was chromatographed on silica with
petroleum ether/CH2Cl2 (8/1) as eluent. The first band gave a trace
of unreacted Ru3(CO)12. The second band afforded complex 1 (169 mg,
84%) as an orange solid. Mp 168À169 °C (dec). Anal. Calcd for C30H17
O9PRu3: C, 42.11; H, 2.00. Found: C, 42.37; H, 2.21. 1H NMR (CDCl3): δ
7.90 (s, 2H, ArÀH), 7.55 (s, 3H, ArÀH), 7.40À7.27 (m, 5H, ArÀH), 7.23
(d, J= 7.2 Hz, 1H, ArÀH), 7.10À6.95 (m, 3H, ArÀH), 4.24 (d, J = 22.1 Hz,
1H, CH2),3.92(d,J= 22.4 Hz, 1H, CH2),À18.16 (d, J= 17.3 Hz, 1H, μ2-H)
ppm. 31P{1H} NMR (CDCl3): δ 35.7 (s) ppm. IR (νCO, cmÀ1): 2085 (s),
2057 (s), 2022 (s), 2002 (s), 1987 (s), 1970 (s), 1960 (s).
Complex 6. Mp 169À170 °C (dec). Anal. Calcd for C26H15O9PRu3:
C, 38.76; H, 1.88. Found: C, 38.99; H, 2.03. 1H NMR (CDCl3): δ 7.68
(d, J = 6.9 Hz, 2H, ArÀH), 7.41À7.34 (m, 3H, ArÀH), 7.02 (d, J =
7.1 Hz, 1H, ArÀH), 6.93 (d, J = 7.2 Hz, 1H, ArÀH), 3.69 (s, 2H, CH2),
2.46 (s, 3H, CH3), 2.38 (s, 3H, CH3) ppm. 31P{1H} NMR (CDCl3): δ
391.8 (s) ppm. IR (νCO, cmÀ1): 2082 (s), 2053 (s), 2027 (s), 2013 (s),
1985 (s).
Reaction of Ru3(CO)12 with (1H-Inden-2-yl)diphenylph-
osphine. Using a procedure similar to that described for the synthesis
of 1, reaction of Ru3(CO)12 (150 mg, 0.235 mmol) and (1H-inden-2-yl)
diphenylphosphine (71 mg, 0.236 mmol) in refluxing octane (30 mL)
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ARTICLE
Table 1. Crystal Data and Summary of X-ray Data Collection
1
2
3
4
5
formula
C
30H17O9PRu3
C30H17O9PRu3
855.62
C24H11O9PRu3
777.51
C26H11O11PRu4
934.60
C32H21O9PRu3
883.67
fw
855.62
T, K
116(2)
113(2)
113(2)
113(2)
113(2)
λ, Å
0.71073
monoclinic
C2/c
0.71073
0.71073
0.71073
0.71075
cryst syst
monoclinic
P21/c
monoclinic
P21/c
triclinic
triclinic
space group
a, Å
P-1
P-1
17.169(3)
17.272(3)
20.228(3)
90
18.744(8)
9.235(4)
20.328(8)
90
12.050(2)
10.849(2)
19.484(4)
90
9.612(5)
11.728(6)
15.382(7)
102.577(6)
97.249(7)
108.782(5)
1565.7(14)
2
10.6366(17)
12.3945(18)
24.119(4)
95.952(3)
98.672(2)
90.097(4)
3126.0(9)
4
b, Å
c, Å
R, deg
β, deg
98.088(2)
90
113.306(6)
90
99.56(3)
90
γ, deg
V, Å3
5938.5(17)
8
3232(2)
4
2511.8(9)
4
Z
Dcalc, g cmÀ3
μ, mmÀ1
1.914
1.759
2.056
1.982
1.878
1.614
1.483
1.896
1.997
1.536
F(000)
3328
1664
1496
892
1728
cryst size, mm
θ range, deg
no. of reflns collected
no. of indep reflns/Rint
no. of params
GOF on F2
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
largest diff. peak and hole (e ÅÀ3
0.30 Â 0.26 Â 0.20
1.68À25.02
20 418
0.20 Â 0.18 Â 0.12
2.03À25.02
21 429
0.20 Â 0.18 Â 0.12
1.71À25.02
13 736
0.22 Â 0.18 Â 0.16
1.91À27.92
19 236
0.26 Â 0.22 Â 0.20
1.65À27.88
29 654
5251/0.0684
393
5691/0.0282
392
4412/0.0406
372
7465/0.0379
379
14 566/0.0358
824
0.770
1.095
1.005
1.027
0.965
0.0442, 0.1154
0.0448, 0.1175
1.077, À1.664
0.0207, 0.0539
0.0225, 0.0545
0.429, À0.575
0.0331, 0.0749
0.0364, 0.0766
1.021, À1.167
0.0250, 0.0629
0.0310, 0.0641
0.775, À0.856
0.0267, 0.0561
0.0347, 0.0586
0.737, À0.700
)
7
8
9
10
11
formula
C28H15O11PRu4
962.65
C28H15O11PRu4
962.65
C32H23O8PRu3
869.68
C30H23O6PRu3
813.66
C31H19O9PRu3
869.64
fw
T, K
113(2)
113(2)
113(2)
113(2)
116(2)
λ, Å
0.71075
0.71075
0.71073
0.71073
0.71073
monoclinic
C2/c
cryst syst
monoclinic
P21/c
triclinic
monoclinic
P21/c
triclinic
space group
a, Å
P-1
P-1
10.2070(10)
15.6790(14)
19.527(2)
90
8.8717(8)
10.0624(9)
16.6570(15)
77.613(5)
85.545(7)
88.201(6)
1447.8(2)
2
11.529(2)
18.246(4)
14.917(3)
90
9.6491(19)
9.951(2)
15.950(3)
86.84(3)
79.00(3)
66.39(3)
1377.1(5)
2
17.663(7)
16.873(6)
20.306(7)
90
b, Å
c, Å
R, deg
β, deg
104.427(5)
90
101.79(3)
90
95.605(5)
90
γ, deg
V, Å3
3026.5(5)
4
3071.6(11)
4
6023(4)
8
Z
Dcalc, g cmÀ3
μ, mmÀ1
2.113
2.208
1.881
1.962
1.918
2.070
2.163
1.559
1.726
1.593
F(000)
1848
924
1704
796
3392
cryst size, mm
θ range, deg
no. of reflns collected
no. of indep reflns/Rint
no. of params
GOF on F2
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
largest diff. peak and hole (e ÅÀ3
0.22 Â 0.18 Â 0.16
1.69À37.83
60 815
0.06 Â 0.04 Â 0.04
1.25À27.95
18 328
0.20 Â 0.06 Â 0.04
2.12À25.02
23 170
0.18 Â 0.16 Â 0.12
2.34À25.02
11 254
0.20 Â 0.14 Â 0.10
1.89À25.02
17 610
15 633/0.0414
399
6905/0.0300
399
5419/0.0376
408
4824/0.0245
364
5153/0.0338
402
1.132
1.007
1.095
1.069
1.138
0.0326, 0.0695
0.0385, 0.0726
0.816, À1.790
0.0241/0.0441
0.0316/0.0459
0.693, À0.619
0.0237, 0.0579
0.0264, 0.0590
0.594, À0.530
0.0231, 0.0580
0.0259, 0.0592
0.997, À0.642
0.0422/0.1436
0.0430/0.1440
1.718, À0.960
)
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ARTICLE
Complex 7. Mp 158À159 °C (dec). Anal. Calcd for C28H15O11PRu4:
C, 34.93; H, 1.57. Found: C, 34.97; H, 1.63. 1H NMR (CDCl3): δ 7.59
(t, J = 8.8 Hz, 2H, ArÀH), 7.42À7.32 (m, 3H, ArÀH), 6.90 (d, J = 6.9
Hz, 1H, ArÀH), 6.79 (d, J = 7.0 Hz, 1H, ArÀH), 5.10 (d, J = 1.4 Hz, 1H,
CH2), 4.76 (s, 1H, CH2), 2.33 (s, 3H, CH3), 2.17 (s, 3H, CH3) ppm.
31P{1H} NMR (CDCl3): δ 432.3 (s) ppm. IR (νCO, cmÀ1): 2082 (s),
2061 (s), 2016 (s), 1992 (s), 1982 (s), 1967 (s), 1943 (s).
in clusters 2 and 4 have been treated by the Platon Squeeze18 routine. All
calculations were carried out using the SHELXL-97 program system. All
non-hydrogen atoms were refined anisotropically. Hydrogen atoms were
assigned idealized positions and were included in structure factor calcula-
tions. The crystal data and summary of X-ray data collection for complexes
1À5, 7À11 are presented in Table 1. In 3, the phenyl group attached to the
P atom is rotational disordered.
Complex 8. Mp 149À150 °C (dec). Anal. Calcd for C28H15O11PRu4:
1
C, 34.93; H, 1.57. Found: C, 35.14; H, 1.70. H NMR (CDCl3): δ
’ ASSOCIATED CONTENT
7.24À7.19 (m, 3H, ArÀH), 6.98 (d, J = 7.5 Hz, 1H, ArÀH), 6.89 (d, J =
7.5 Hz, 1H, ArÀH), 6.68 (dd, J = 7.0, 14.4 Hz, 2H, ArÀH), 3.17 (s, 3H,
CH3), 2.83 (s, 2H, CH2), 1.95 (s, 3H, CH3) ppm. 31P{1H} NMR
(CDCl3): δ 269.1 (s) ppm. IR (νCO, cmÀ1): 2078 (m), 2024 (s), 2002
(s), 1971 (s), 1842 (m).
S
Supporting Information. Crystallographic details for
b
1À5 and 7À11 in CIF format. This material is available free of
charge via the Internet at http://pubs.acs.org.
Reaction of Ru3(CO)12 with (3,4,7-Trimethyl-1H-inden-1-
yl)diphenylphosphine. A solution of Ru3(CO)12 (120 mg, 0.188
mmol) and (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine (193
mg, 0.564 mmol) in toluene (20 mL) was refluxed for 4 h to give a
dark solution. After removal of solvent in vacuo, the residue was
chromatographed on silica with petroleum ether/CH2Cl2 (8/1) as
eluent. The first band gave 17 mg (10%) of complex 9 as a yellow solid.
The second band afforded 23 mg (15%) of complex 10 as a red solid.
Complex 9. Mp 172À173 °C (dec). Anal. Calcd for C32H23O8PRu3:
C, 44.19; H, 2.67. Found: C, 43.79; H, 2.31. 1H NMR (CDCl3): δ 7.97
(t, J = 8.0, 9.6 Hz, 2H, ArÀH), 7.67À7.60 (m, 3H, ArÀH), 7.20À7.10
(m, 2H, ArÀH), 7.02À6.96 (m, 2H, ArÀH), 6.77 (d, J = 7.5 Hz, 1H,
ArÀH), 6.47 (d, J = 7.5 Hz, 1H, ArÀH), 6.07 (d, J = 14.0 Hz, 1H,
ArÀH), 3.79 (d, J = 3.6 Hz, 1H, CH), 2.60 (d, J = 9.5 Hz, 1H, CH2), 2.52
(d, J = 9.5 Hz, 1H, CH2), 2.51 (s, 3H, CH3), 1.71 (s, 3H, CH3), À14.41
(d, J = 16.0 Hz, 1H, μ2-H), À16.30 (s, 1H, μ2-H) ppm. 31P{1H} NMR
(CDCl3): δ 15.5 (s) ppm. IR (νCO, cmÀ1): 2078 (s), 2048 (s), 2017 (s),
2000 (s), 1988 (s), 1977 (s), 1959 (s), 1948 (s).
Complex 10. Mp 195À196 °C (dec). Anal. Calcd for C30H23O6-
PRu3: C, 44.28; H, 2.85. Found: C, 43.90; H, 2.59. 1H NMR (CDCl3): δ
8.23À8.17 (m, 2H, ArÀH), 7.51 (t, J = 6.9, 7.1 Hz, 2H, ArÀH), 7.45 (d,
J = 7.0 Hz, 1H, ArÀH), 7.24À7.16 (m, 3H, ArÀH), 6.93À6.88 (m, 2H,
ArÀH), 5.29 (d, J= 1.4 Hz, 1H, ArÀH), 4.96 (d, J= 6.5 Hz, 1H, C5-ring H),
4.52 (d, J = 6.3 Hz, 1H, C5-ring H), 4.39 (d, J = 1.6 Hz, 1H, ArÀH), 2.74
(s, 3H, CH3), 2.48 (s, 3H, CH3), 1.78 (s, 3H, CH3) ppm. 31P{1H} NMR
(CDCl3): δ 216.5 (s) ppm. IR (νCO, cmÀ1): 2011 (s), 1976 (s), 1924 (s),
1914 (s).
Reaction of Ru3(CO)12 with (3-Methyl-1H-inden-1-yl)diph-
enylphosphine. A solution of Ru3(CO)12 (120 mg, 0.188 mmol) and
(3-methyl-1H-inden-1-yl)diphenylphosphine (60 mg, 0.190 mmol) in
toluene (20 mL) was refluxed for 4 h to give a dark brown solution. After
removal of solvent in vacuo, the residue was chromatographed on silica
with petroleum ether/CH2Cl2 (5/1) as eluent. The major band gave 15
mg (9%) of complex 11 as an orange solid. Mp 170À171 °C (dec). Anal.
Calcd for C31H19O9PRu3: C, 42.81; H, 2.20. Found: C, 42.93; H, 2.43.
1H NMR (CDCl3): δ 7.88 (s, 2H, ArÀH), 7.54 (s, 3H, ArÀH),
7.42À7.28 (m, 6H, ArÀH), 7.22 (d, J = 6.2 Hz, 1H, ArÀH), 7.07À6.99
(m, 2H, ArÀH), 3.98 (q, J=7.2Hz, 1H, CH), 0.99(d, J= 7.0 Hz, 3H, CH3),
À18.25 (d, J= 18.3 Hz, 1H, μ2-H) ppm. 31P{1H} NMR (CDCl3):δ36.4(s)
ppm. IR (νCO, cmÀ1): 2085 (s), 2057 (s), 2021 (s), 2001 (s), 1987 (s), 1971
(s), 1957 (s).
Crystallographic Studies. Single crystals suitable for X-ray dif-
fraction analysis were grown from hexane/CH2Cl2 (for 1, 2, 5, and
8À11) and hexane (for 7) solution at room temperature, or from hexane
(for 3) and toluene/CH2Cl2 (for 4) solution at À20 °C. Data collection
was performed on a Rigaku Saturn 70 diffractometer equipped with a
rotating anode system by using graphite-monochromated Mo KR
radiation (ωÀ2θ scans). Semiempirical absorption corrections were
applied for all complexes. The structures were solved by direct methods
and refined by full-matrix least-squares. The disordered solvent molecules
’ AUTHOR INFORMATION
Corresponding Author
*Fax: 86-22-23504781. E-mail: bqwang@nankai.edu.cn.
’ ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China
(nos. 20872066, 21072101, and 20721062) for financial support.
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