Synthesis and characterization of the first transition-metal fullerene complexes containing bis(η6-benzene)chromium moieties

Article abstract of DOI:10.1016/j.jorganchem.2005.10.020

While photochemical reaction of C₆₀ with an equimolar amount of Mo(CO)₄(η⁶-Ph₂PC₆H ₅)₂Cr (1) in toluene at room temperature produced bimetallic Mo/Cr fullerene complex fac/mer-(η

Full text of DOI:10.1016/j.jorganchem.2005.10.020

Journal of Organometallic Chemistry 691 (2006) 787–792
www.elsevier.com/locate/jorganchem
Synthesis and characterization of the first transition-metal
fullerene complexes containing bis(g6-benzene)chromium moieties
a,
a
a
b
Li-Cheng Song *, Guang-Ao Yu , Qing-Mei Hu , Chi-Ming Che ,
b
b,
*
Nianyong Zhu , Jie-Sheng Huang
a
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
Department of Chemistry, The HKU-CAS Joint Laboratory on New Material, The University of Hong Kong, Pokfulam Road, Hong Kong, China
b
Received 2 June 2005; received in revised form 8 October 2005; accepted 13 October 2005
Available online 5 December 2005
Abstract
While photochemical reaction of C60 with an equimolar amount of Mo(CO)4(g6-Ph2PC6H5)2Cr (1) in toluene at room temperature
produced bimetallic Mo/Cr fullerene complex fac/mer-(g2-C60)Mo(CO)3[(g6-Ph2PC6H5)2Cr] (2) in 87% yield, the thermal reaction of an
equimolar mixture of C60, M(dba)2 (M = Pd, Pt; dba = dibenzylideneacetone) and (g6-Ph2PC6H5)2Cr (3) in toluene at room temperature
afforded bimetallic M/Cr fullerene complexes (g2-C60)M[(g6-Ph2PC6H5)2Cr] (4, M = Pd; 5, M = Pt) in 88% and 92% yields, respectively.
Products 2, 4 and 5 are the first transition-metal fullerene complexes containing bis(g6-benzene)chromium moieties. While 2, 4 and 5
were characterized by elemental analysis and spectroscopy, the crystal molecular structures of 4 along with the starting materials 1
and 3 have been determined by X-ray diffraction techniques.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Molybdenum; Platinum; Palladium; [60]Fullerene; Bis(g6-diphenylphosphinobenzene)chromium; Crystal structures
1. Introduction
(M = Pd, Pt) [10], and (g2-C60)M[(g5-Ph2PC5H4)2Co]+-
(PF6)À (M = Pd, Pt) [10]. However, up to now, no report
has appeared regarding another series of transition metal
fullerene complexes in which a transition-metal atom is
sandwiched between two parallel benzene rings, such as
bis(g6-benzene)chromium. Now, as a continuation of our
project regarding the metallocene-containing transition-
metal fullerene complexes, we report a new series of transi-
tion-metal fullerene complexes, each of which contains a
bis(g6-benzene)chromium unit, namely fac/mer-(g2-C60)-
Mo(CO)3[(g6-Ph2PC6H5)2Cr] (2) and (g2-C60)M[(g6Ph2-
PC6H5)2Cr] (4, M = Pd; 5, M = Pt). Apparently, these
complexes are of particular interest, since they contain both
theoretically and practically important fullerene core and
sandwich moiety. Furthermore, we also report the crystal
molecular structure of 4, as well as those of the starting
materials Mo(CO)4[(g6-Ph2PC6H5)2Cr] (1) and (g6-Ph2-
PC6H5)2Cr (3).
Since the discovery of [60]fullerene [1] and its synthesis in
macroscopic quantities [2], a great number of transition-
metal fullerene complexes have been synthesized and struc-
turally characterized [3–6], largely because of their unique
structures, novel properties and the potential applications
in various fields such as material and life sciences [7].
Recently, we reported a series of transition-metal fullerene
complexes which contain a bis(g5-cyclopentadienyl)-type
of metallocene unit, such as (g2-C60)M(CO)3[(g5-Ph2-
PC5H4)2Fe] (M = Mo, W) [8], (g2-Cn)Pt[(g5-Ph2AsC5H4)2-
Fe] (Cn = C60, C70) [9], (g2-C60)M[(g5-Ph2PC5H4)2Ru]
*
Corresponding authors. Fax: +86 022 23504853.
E-mail addresses: lcsong@nankai.edu.cn (L.-C. Song), jshuang@
hkucc.hku.hk (J.-S. Huang).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.10.020

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L.-C. Song et al. / Journal of Organometallic Chemistry 691 (2006) 787–792
2. Results and discussion
2.1. Synthesis and characterization of fac/mer-
(g2-C60)Mo(CO)3[(g6-Ph2PC6H5)2Cr] (2) and
(g2-C60)M[(g6-Ph2PC6H5)2Cr] (4, M = Pd; 5, M = Pt)
We found that the bimetallic Mo/Cr fullerene complex 2
could be obtained in 87% yield when an equimolar mixture
of C60 and Mo(CO)4[(g6-Ph2PC6H5)2Cr] (1) was irradiated
with a UV 450 W photochemical lamp in toluene at room
temperature for 2 h (Scheme 1).
Compound 2 is an air-sensitive, dark green solid, which
1
has been characterized by elemental analysis, and IR, H
NMR, 31P NMR, and UV–Vis spectroscopy. The 31P
NMR spectrum of 2 showed it to be an isomeric mixture
of the fac and mer isomers. This is because that the 31P
NMR spectrum (Fig. 1) displayed two doublets at 39.18
and 29.84 ppm assignable to the two different P atoms in
the mer isomer and one singlet at 33.49 ppm attributable
to the two identical P atoms in the fac isomer. The IR spec-
trum of 2 exhibited four absorption bands in the range
1433–526 cmÀ1 for its C60 core[11] and six bands in the
region 2043–1889 cmÀ1 for its terminal carbonyls. The lat-
ter is in good agreement with 2 being a mixture of the two
isomers, since the number of IR active bands cannot exceed
but may be less than the number of CO ligands in the com-
plex [12]. The UV–Vis spectrum of 2 showed three intense
bands between 200 and 400 nm, which are close to those of
free C60 [13]. Compared with that of free C60, the UV–Vis
spectrum of 2 has a new weak broad band appearing at
435 nm , which might be attributed to the [60]fullerene cage
being coordinated to molybdenum in an g2-fashion [14].
Fig. 1. 31P NMR spectrum of 2.
(4, M = Pd; 5, M = Pt) in 88% and 92% yields, respectively
(Scheme 2).
The synthetic route for formation of 4 and 5 is believed
to involve an initial reaction of C60 with M(dba)2 to give
(C60M)n (M = Pd [15], Pt [16]) and the subsequent reaction
of (C60M)n with diphosphine ligand (g6-Ph2PC6H5)2Cr (3).
Products 4 and 5 are air-sensitive, green solids, which were
characterized by elemental analysis and spectroscopy. For
example, both IR spectra of 4 and 5 (showing four absorp-
tion bands in the region 1435–523 cmÀ1) [11] and UV–Vis
spectra of 4 and 5 (displaying three intense bands in the
range 200–400 nm and one weak broad band at ca.
440 nm) are consistent with their C60 ligand being coordi-
nated to Pd or Pt in an g2-mode [11,13,14]. In addition,
1
The H NMR spectrum of 2 displayed three sharp singlets
at 3.69, 3.97 and 4.23 ppm, which can be assigned respec-
tively to c-CH, b-CH and a-CH of the two benzene rings
in the bis(benzene)chromium moiety.
We further found that the thermal reaction of an equi-
molar mixture of C60, M(dba)2 (M = Pd, Pt; dba = diben-
zylideneacetone) and (g6-Ph2PC6H5)2Cr (3) in toluene at
room temperature resulted in formation of the bimetallic
M/Cr fullerene complexes (g2-C60)M[(g6-Ph2PC6H5)2Cr]
1
the H NMR spectra of 4 and5 exhibited three singlets at
3.70, 3.97 and 4.23 ppm assigned to c-CH, b-CH and a-
CH of the two benzene rings in bis(benzene)chromium
unit, respectively. However, it is worth pointing out that
although the 31P NMR spectrum of 4 showed one singlet
at 29.62 ppm for its two identical P atoms, the qualified
31P NMR spectrum of 5 was not obtained due to its too lit-
tle solubility in common deuterated organic solvent.
C60 Mo(CO)4[(η6 Ph2PC H5)2Cr]
1
toluene
hv
2.2. Crystal structures of 3, 1 and 4
Although the Ph2P-disubstituted bis(g6-benzene)chro-
mium (g6-Ph2PC6H5)2Cr (3) and its molybdenum complex
CO
Mo
CO
Ph2
P
OC
Ph2
P
Ph2
P
Cr
OC
OC
P
Ph2
Cr
Mo
CO
toluene
r. t.
Cr
M
6
C60
M(dba)2
(
Ph2PC6H5)2Cr
η
P
Ph2
P
Ph2
3
mer isomer
2
fac isomer
2
4 M = Pd
5 M = Pt
Scheme 1.
Scheme 2.

L.-C. Song et al. / Journal of Organometallic Chemistry 691 (2006) 787–792
789
Mo(CO)4[(g6-Ph2PC6H5)2Cr] (1) were known three dec-
Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for 1
˚
Bond lengths (A)
ades ago [17,18], there are no crystallographic data of 3
and 1 available in the literature. Fortunately, we have
succeeded in determining their molecular structures by
single-crystal X-ray diffraction techniques. The molecular
structures of 3 and 1 are shown in Figs. 2 and 3, whereas
Tables 1 and 2 list their selected bond lengths and angles,
respectively. As can be seen in Fig. 2, diphosphine ligand
3 is centrosymmetric with respect to Cr(1) atom. Therefore,
the two benzene rings are parallel and staggered to each
Mo(1)–C(1)
Mo(1)–C(2)
Mo(1)–C(3)
Mo(1)–C(4)
Mo(1)–P(1)
2.018(7)
2.006(8)
2.031(8)
1.986(8)
2.558(3)
Mo(1)–P(2)
Cr(1)–C(5)
Cr(1)–C(8)
P(1)–C(11)
P(2)–C(5)
2.552(3)
2.125(4)
2.143(4)
1.875(4)
1.864(4)
Bond angles (ꢁ)
P(2)–Mo(1)–P(1)
C(4)–Mo(1)–C(2)
C(4)–Mo(1)–C(1)
C(2)–Mo(1)–C(1)
C(1)–Mo(1)–C(3)
C(2)–Mo(1)–C(3)
100.21(11)
86.5(3)
C(2)–Mo(1)–P(2)
C(1)–Mo(1)–P(2)
C(3)–Mo(1)–P(1)
C(4)–Mo(1)–P(1)
C(2)–Mo(1)–P(1)
C(1)–Mo(1)–P(1)
88.3(2)
91.4(2)
91.5(2)
85.1(3)
170.9(2)
89.6(2)
87.5(3)
93.3(3)
178.8(3)
85.6(3)
other, the distances from Cr(1) atom to the two centroids
˚
of two benzene rings are equal (1.611 A) and the two
Ph2P substituents are trans to each other with respect to
the central Cr(1) atom.
Interestingly, as shown in Fig. 3, the diphosphine ligand
3 in complex 1 is chelated via its two P atoms to the Mo
atom of the Mo(CO)4 moiety, thus completing a cis octahe-
dral coordination geometry for the Mo atom. However, the
configuration at the Mo atom is distorted from a normal
octahedral geometry, with the P(1)–Mo(1)–P(2) angle of
100.21(11)ꢁ increased from the ideal value of 90ꢁ and larger
than that of Mo(CO)4(dppf) (95.28(2)ꢁ) [19]. The chelated
ligand 3 has two parallel benzene rings (with a dihedral
angle of only 0.5ꢁ), which are staggered to each other. In
addition, the two distances between Cr(1) atom and the
Fig. 2. ORTEP plot of 3 with the atom labeling scheme.
˚
centroids of the two benzene rings are equal to 1.612(7) A.
Particularly interesting is that product 4 is the first syn-
thesized and crystallographically characterized transition-
metal fullerene complex containing a bis(g6-benzene)metal
moiety. As can seen in Fig. 4, product 4 has a C60 ligand
bonded to Pd(1) atom in an g2-fashion with the C(1)–
C(2) bond between two six-membered rings (see Table 3).
˚
The C(1)–C(2) bond length (1.466(5) A) is actually the
same as the corresponding that in (g2-C60)Pd(dppf)
Fig. 3. ORTEP plot of 1 with the atom labeling scheme.
˚
(1.466(11) A), but considerably longer than the 6:6 bond
˚
length in free C60 (1.38 A) [20], obviously due to metal-
to-C60 p-back-donation. In addition, the Ph2P-disubsti-
tuted bis(g6-benzene)chromium ligand 3 is chelated via
its two P atoms to Pd(1) atom. The zerovalent Pd(1) is at
the center of a tetragon constituted by C(1), C(2), P(1)
and P(2) atoms, and all the five atoms are almost coplanar
Table 1
˚
Selected bond lengths (A) and angles (ꢁ) for 3
˚
Bond lengths (A)
Cr(1)–C(3)
Cr(1)–C(2)
Cr(1)–C(6)
Cr(1)–C(5)
Cr(1)–C(1)
Cr(1)–C(4)
2.131(4)
2.133(4)
2.132(3)
2.139(4)
2.147(4)
2.148(4)
P(1)–C(1)
P(1)–C(13)
P(1)–C(7)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
1.821(4)
1.828(4)
1.836(4)
1.420(5)
1.395(6)
1.395(6)
˚
with a mean deviation of 0.0493 A. The two bond
angles P(1)–Pd(1)–P(2) (106.50(3)ꢁ) and C(1)–Pd(1)–C(2)
(40.39(12)ꢁ) are very close to the corresponding those in
(g2-C60)Pd(dppf) (103.30(9) and 40.8(3), respectively) [9].
While the distances from Cr(1) atom to the two centroids
Bond angles (ꢁ)
C(3)–Cr(1)–C(1)
C(2)–Cr(1)–C(1)
C(6)–Cr(1)–C(1)
C(5)–Cr(1)–C(1)
C(1)–Cr(1)–C(4)
C(5)–C(4)–C(3)
69.81(16)
38.76(14)
38.53(14)
69.63(16)
82.14(16)
120.3(5)
C(1)–P(1)–C(13)
C(1)–P(1)–C(7)
C(6)–C(1)–C(2)
C(6)–C(1)–P(1)
C(2)–C(1)–P(1)
C(3)–C(2)–C(1)
105.94(18)
100.60(17)
118.4(4)
125.6(3)
115.9(3)
120.8(4)
˚
of the two benzene rings are 1.632(3) A, the two benzene
rings are parallel and arranged in a staggered manner.
˚
The distance between Pd(1) and Cr(1) is 4.396(1) A, which
is far greater than the sum of their van der Waals radii and
thus no metal–metal interactions between these two metal

790
L.-C. Song et al. / Journal of Organometallic Chemistry 691 (2006) 787–792
Fig. 4. ORTEP plot of 4 with the atom labeling scheme.
Table 3
trophotometer and IR spectra on a Bio-Rad FTS 135 spec-
trophotometer. Elemental analysis was performed on an
Elementar Vario EL analyzer. Melting points were deter-
mined on a Yanaco MP-500 apparatus.
˚
Selected bond lengths (A) and angles (ꢁ) for 4
˚
Bond lengths (A)
Pd(1)–C(2)
Pd(1)–C(1)
Pd(1)–P(1)
Cr(1)–C(62)
Cr(1)–C(67)
2.116(3)
2.129(3)
2.3341(10)
2.133(3)
2.136(3)
P(1)–C(61)
P(2)–C(67)
Pd(1)–P(2)
C(1)–C(2)
Cr(1)–C(61)
1.817(3)
1.824(3)
2.3410(11)
1.466(5)
2.138(3)
3.1. Preparation of fac/mer-(g2-C60)Mo(CO)3-
[(g6-Ph2PC6H5)2Cr] (2)
Bond angles (ꢁ)
C(2)–Pd(1)–C(1)
C(2)–Pd(1)–P(1)
C(62)–Cr(1)–C(61)
C(1)–Pd(1)–P(2)
C(1)–Pd(1)–P(2)
C(62)–Cr(1)–C(67)
A 100-ml photoreactor equipped with a N2 inlet tube and
a serum cap was charged with 0.044 g (0.06 mmol) of C60,
0.039 g (0.05 mmol) of Mo(CO)4[(g6-Ph2PC6H5)2Cr], and
30 ml of toluene. The photoreactor containing the resulting
purple solution was irradiated under N2 by a water-cooled
UV 450 W mercury vapor lamp for 2 h to give a dark green
solution. Solvent was removed at reduced pressure, leaving
a solid which was washed with 20 ml of toluene and 10 ml of
hexane successively, and finally dried in vacuo to give
0.064 g (87%) of 2 as a dark green solid. m.p. > 300 ꢁC.
Anal. Found: C, 80.39; H, 2.04%. C99H30CrMoO3P2 Calc.:
C, 80.50; H, 2.05. IR (KBr disk): mC„O 2043s, 1997s, 1980m,
40.39(12)
106.46(9)
38.71(12)
70.27(19)
106.76(10)
135.19(13)
P(1)–Pd(1)–P(2)
C(61)–P(1)–C(73)
C(61)–P(1)–Pd(1)
C(79)–P(1)–Pd(1)
C(67)–P(2)–C(91)
C(2)–C(1)–Pd(1)
106.50(3)
106.76(15)
114.36(10)
115.32(10)
104.84(16)
69.34(18)
centers. Similar cases were seen in its bis(g5-cyclopentadie-
nyl)metal analogues, such as (g2-C60)Pd(dppf) (PdÁ Á ÁFe =
2
˚
˚
4.196 A) [9], (g -C60)Pd(dppr) (PdÁ Á ÁRu = 4.276 A) [10]
and [(g2-C60)Pd(dppc)]+(PF6)À (PdÁ Á ÁCo = 4.113 A) [10].
˚
1
3. Experimental
1920s, 1889m; mC60 1433m, 1182m, 576m, 526s cmÀ1. H
NMR (200 MHz, CDCl3): d 3.69 (s, 2H, c-CH), 3.97(s,
4H, b-CH), 4.23(s, 4H, a-CH), 7.26–7.42 (m, 20H,
4C6H5).31P NMR (81.0 MHz, CDCl3, H3PO4): d 29.84 (d,
All reactions were carried out under highly purified
nitrogen atmosphere using standard Schlenk or vacuum-
line techniques. Toluene and hexane were distilled from
Na/benzophenone ketyl. Other solvents were bubbled with
nitrogen for at least 15 min before use. (g6-Ph2PC6H5)2Cr
[17], Mo(CO)4[(g6-Ph2PC6H5)2Cr] [18], Pd(dba)2 [21], and
Pt(dba)2 [22] were prepared according to the literature
methods. C60 (99.9%) was available commercially. 1H
NMR and 31P NMR were recorded on a Bruker AC-
P200 spectrometer. UV–Vis on a Shimadzu TU 1901 spec-
1P, JP–P = 31.7 Hz), 33.49 (s, 2P), 39.18 (d, 1P, JP–P
=
31.7 Hz). UV–Vis (C6H5Me): kmax (loge) 284.2 (4.62),
285.8 (4.61), 334.2 (4.44), 435.0 (3.90) nm.
3.2. Preparation of (g2-C60)Pd[(g6-Ph2PC6H5)2Cr] (4)
A 100-ml three-necked flask equipped with a magnetic
stir-bar, a rubber septum and a nitrogen inlet tube was

L.-C. Song et al. / Journal of Organometallic Chemistry 691 (2006) 787–792
791
charged with 0.036 g (0.05 mmol) of C60, 0.030 g
3.4. X-ray crystal structure determinations of 3 and 1
(0.05 mmol) of (g6-Ph2PC6H5)2Cr and 20 ml of toluene.
To the purple toluene solution was added 0.029 g
(0.05 mmol) of Pd(dba)2. The mixture was stirred at room
temperature for 0.5 h to give a deep green suspension, and
then the suspension was carefully layered with 40 ml of
hexane overnight to give a precipitate. The precipitate
was filtered, washed with 40 ml of hexane and dried in
vacuo to afford 0.062 g (88%) of 4 as a green solid.
m.p. > 300 ꢁC. Anal. Found: C, 81.99; H, 2.15%.
C96H30CrP2Pd Calc.: C, 82.15; H, 2.15. IR (KBr disk):
Single-crystals of 3 and 1 suitable for X-ray diffraction
analyses were obtained by slow diffusion of hexane into
their toluene solutions at room temperature. The single-
crystal of 3 or 1 was glued to a glass fiber and mounted
on a Bruker SMART 1000 automated diffractometer. Data
were collected using graphite-monochromatized Mo Ka
˚
radiation (k = 0.71073 A) at room temperature in the x–
2h scanning mode. Absorption correction was performed
with SADABS [23]. The structure was solved by direct meth-
ods using the SHELXS-97 program and refined by full-matrix
least-squares techniques (SHELXL-97) on F2 [24]. Hydrogen
atoms were located by using the geometric method. All cal-
culations were performed on a Bruker Smart computer.
Details of the crystals, data collections, and structure
refinements are summarized in Table 4.
mC60 1435m, 1184m, 575m, 523s cmÀ1
.
1H NMR
(200 MHz, CDCl3): d 3.73 (s, 2H, c-CH), 3.97 (s, 4H, b-
CH), 4.23 (s, 4H, a-CH), 7.26–7.32 (m, 20H, 4C6H5). 31P
NMR (81.0 MHz, benzene-d6, H3PO4): d 29.62 (s, 2P).
UV–Vis (C6H5Me): kmax (loge) 281.7 (4.73), 284.2 (4.74),
331.7 (4.96), 440.8 (3.48) nm.
3.3. Preparation of (g2-C60)Pt[(g6-Ph2PC6H5)2Cr] (5)
3.5. X-ray crystal structure determination of 4
Similarly, when using 0.033 g (0.05 mmol) of Pt(dba)2,
0.069 g (92%) of 5 as a green solid was prepared .
m.p. > 300 ꢁC. Anal. Found: C, 77.33; H, 2.05%.
C96H30CrP2Pt Calc.: C, 77.27; H, 2.03. IR (KBr disk):
The X-ray qualified single-crystals of 4 were obtained by
slow diffusion of hexane into its toluene solution at room
temperature. Data were collected using graphite-mono-
˚
chromatized Mo Ka radiation (k = 0.71073 A) at À20 ꢁC
mC60 1434m, 1183m, 575m, 526s cmÀ1
.
1H NMR
on a MAR diffractometer with a 300-mm image plate
detector, Data collection was made with 2ꢁ oscillation step
of u, 120 s exposure time and scanner distance at 120 mm.
90 images were collected. The structure was solved by
direct methods employing SHELXS-97 program [25a] and
(200 MHz, CDCl3): d 3.69 (s, 2H, c-CH), 3.97 (s, 4H, b-
CH), 4.23 (s, 4H, a-CH), 7.26–7.28 (m, 20H, 4C6H5).
UV–Vis (C6H5Me): kmax (loge) 281.7 (4.75), 284.2 (4.75),
332.5 (4.89), 436.7 (3.64) nm.
Table 4
Crystal data and structural refinements details for 3, 1 and 4
3
1
4
Formula
C
576.54
293(2)
Monoclinic
P2(1)/c
8.721 (3)
36H30CrP2
C47H38CrMoO4P2
876.65
293(2)
C109H52CrP2Pd
1581.85
253(2)
Monoclinic
P21/c
14.122(3)
Formula weight
Temperature (K)
Crystal system
Space group
Triclinic
ꢀ
P1
˚
a (A)
11.357(16)
˚
b (A)
18.732(6)
9.025(3)
12.572(18)
14.37(2)
24.509(5)
20.023(4)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
93.55(3)
95.87(2)
93.50(3)
2033(5)
90
99.22(3)
90
6841(2)
101.694(6)
90
1443.7(8)
3
˚
V (A )
Z
2
2
4
Dcalc (g cmÀ3
)
1.326
0.531
0.40 · 0.30 · 0.10
600
1.432
0.698
0.20 · 0.20 · 0.10
896
1.536
0.529
0.35 · 0.25 · 0.15
3224
l (Mo Ka) (mmÀ1
Crystal size (mm)
F(000)
)
2hmax (ꢁ)
50.06
5902
2552
50.06
8101
6828
51.24
40534
11708
No. of observations
No. of independent observations
Index ranges
À10 6 h 6 9,
À21 6 k 6 22, À10 6 l 6 9
0.956
À13 6 h 6 13,
À14 6 k 6 9, À16 6 l 6 17
0.999
À16 6 h 6 16,
À29 6 k 6 29, À24 6 l 6 24
0.988
Goodness-of-fit
R
Rw
0.0473
0.1042
0.591 and À0.290
0.0640
0.1496
0.900 and À1.001
0.0432
0.1212
0.791 and À0.823
À3
˚
Largest difference peak and hole (e A
)

792
L.-C. Song et al. / Journal of Organometallic Chemistry 691 (2006) 787–792
refined by full-matrix least-squares on F2 employing
SHELXS-97 program [25b] on PC. In the least-squares refine-
ments, all non-hydrogen atoms were refined anisotropi-
cally, and the H atoms at calculated positions were not
refined. Details of the crystal, data collection, and structure
refinement are summarized in Table 4.
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4. Supplementary material
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Crystallographic data for the structures reported in this
paper have been deposited with the Cambridge Crystallo-
graphic Data Centre, CCDC nos. 271997 for 3, 271998
for 1 and 273171 for 4. Copies of this information may
be obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: +44 1223
336 033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
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Acknowledgments
We are grateful to the National Natural Science Foun-
dation of China, the Research Fund for the Doctoral Pro-
gram of Higher Education of China, and the Hong Kong
Research Grants Council (HKU 7026/04P) for financial
support of this work.
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