Synthesis and structural characterization of the μ-η1: η5-Ph2PC5H4 ligand-containing transition-metal cluster and dinuclear complexes

Article abstract of DOI:10.1021/om070020a

The isolobal displacement reaction of tetrahedral cluster (μ₃-S)FeCo₂(CO)₉ with isolobal reagents η⁵-Ph₂PC₅H₄(CO)₃MLi (M = Mo, W) in THF at about 60 °C was found to gi

Full text of DOI:10.1021/om070020a

1966
Organometallics 2007, 26, 1966-1971
Synthesis and Structural Characterization of the µ-η1:η5-Ph2PC5H4
Ligand-Containing Transition-Metal Cluster and Dinuclear
Complexes (µ-η1:η5-Ph2PC5H4)(µ3-S)MFeCo(CO)7 (M ) Mo, W),
(µ-η1:η5-Ph2PC5H4)(µ3-RC)MCo2(CO)7 (M ) Mo, W; R ) Me, Ph),
and (µ-η1:η5-Ph2PC5H4)CpMo2(CO)5 Obtained from the Studied
Isolobal Displacement Reactions
Li-Cheng Song,* Guang-Ao Yu, Yang Liu, Bang-Shao Yin, Xiao-Guang Zhang, and
Qing-Mei Hu
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai UniVersity,
Tianjin 300071, People’s Republic of China
ReceiVed January 8, 2007
The isolobal displacement reaction of tetrahedral cluster (µ3-S)FeCo2(CO)9 with isolobal reagents η5-
Ph2PC5H4(CO)3MLi (M ) Mo, W) in THF at about 60 °C was found to give the µ-η1:η5-Ph2PC5H4-
containing tetrahedral clusters (µ-η1:η5-Ph2PC5H4)(µ3-S)MFeCo(CO)7 (1, M ) Mo; 2, M ) W), whereas
tetrahedral clusters (µ3-RC)Co3(CO)9 (R ) Me, Ph) reacted with η5-Ph2PC5H4(CO)3MLi under the same
conditions to afford the corresponding tetrahedral clusters (µ-η1:η5-Ph2PC5H4)(µ3-MeC)MCo2(CO)7 (3,
M ) Mo; 4, M ) W) and (µ-η1:η5-Ph2PC5H4)(µ3-PhC)MCo2(CO)7 (5, M ) Mo; 6, M ) W). However,
it was found that when tetrahedral cluster CpMoCo3(CO)11 reacted with isolobal reagent η5-Ph2PC5H4(CO)3-
MoLi under similar conditions, the corresponding tetrahedral cluster (µ-η1:η5-Ph2PC5H4)CpMo2Co2(CO)9
(7) was not produced, but instead the dinuclear complex (µ-η1:η5-Ph2PC5H4)CpMo2(CO)5 (8) was obtained
unexpectedly. While 1-6 and 8 have been characterized by elemental analysis and spectroscopy, as well
as by X-ray crystallography for 1-3 and 8, the possible pathways for formation of these products are
suggested.
single tetrahedral (µ3-E)MFe2 (E ) S, Se; M ) Mo, W) cluster
complexes obtained from the corresponding single isolobal
displacement reactions,13 the double tetrahedral (µ3-S)MFeCo
(M ) Mo, W) cluster complexes produced from the corre-
sponding double isolobal displacement reactions,14 and the single
or double tetrahedral (µ3-S)M2Fe (M ) Mo, W) cluster core-
containing macrocyclic complexes yielded from the cyclization
isolobal displacement reactions.15-17 On the basis of our
previous studies, we recently carried out a study on isolobal
reactions of the tetrahedral (µ3-S)FeCo2, (µ3-RC)Co3, (R ) Me,
Ph), or MoCo3 cluster core-containing complexes with isolobal
reagents η5-Ph2PC5H4(CO)3MLi (M ) Mo, W). The main
purpose of this study is (i) to see the scope and limitations of
the common isolobal displacement reactions between d9-ML3
and d5-ML5 fragments present in the substrates and the isolobal
reagents; (ii) to see if the Ph2P-substituted Cp ring of the isolobal
reagents could influence the isolobal reactions to give unex-
pected cluster products; and (iii) to develop synthetic methodol-
ogy for preparation of transition-metal cluster complexes. Herein
we report our results obtained from this study.
Introduction
The synthesis and characterization of transition-metal di-
nuclear and cluster complexes have received considerable
attention, because of their interesting chemistry and particularly
their important applications in catalysis and material and life
sciences.1-11 In recent years we have prepared a variety of
transition-metal tetrahedral cluster complexes through isolobal
displacement reactions under the guidance of the principle of
isolobal analogy.12 These complexes include, for example, the
* To whom correspondence should be addressed. Fax: 0086-22-
23504853. E-mail: lcsong@nankai.edu.cn.
(1) Roberts, D. R.; Geoffroy, G. L. In ComprehesiVe Organometallic
Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon
Press: Oxford, England, 1982; Vol. 6, pp 763-877.
(2) Adams, R. D. In ComprehesiVe Organometallic Chemistry II; Abel,
E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford,
England, 1995; Vol. 10, p 1.
(3) Vahrenkamp, H. In Transition Metal Chemistry-Current Problems
of General, Biological and Catalytic ReleVance; Mu¨ller, A., Diemann, E.,
Eds.; Verlag Chemie, 1981; p 35.
(4) Berg, J. M.; Holm, R. H. In Iron-Sulfur Proteins; Spiro, T. G., Ed.;
Wiley: New York, 1982; pp 1-66.
(5) Seyferth, D. AdVances in Organometallic Chemistry; Academic
Press: Inc.: New York, 1976; Vol. 14, p 97.
(6) Seyferth, D.; Henderson, R. S.; Song, L.-C. Organometallics 1982,
1, 125.
(7) Ogino, H.; Inomata, S.; Tobita, H. Chem. ReV. 1998, 98, 2093.
(8) Gladfelter, W. L.; Roesselet, K. J. In The Chemistry of Metal Cluster
Complexes; Shriver, D. F., Kaesz, H. D., Adams, R. D., Eds.; VCH: New
York, 1990; Chapter 7.
(12) Hoffmann, R. Angew. Chem., Int. Ed. Engl. 1982, 21, 711.
(13) Song, L.-C.; Dong, Y.-B.; Hu, Q.-M.; Gao, W.-Q.; Guo, D.-S.; Liu,
P.-C.; Huang, X.-Y.; Sun, J. Organometallics 1999, 18, 2168.
(14) Song, L.-C.; Shen, J.-Y.; Hu, Q.-M.; Huang, X.-Y. Organometallics
1995, 14, 98.
(15) Song, L.-C.; Guo, D.-S.; Hu, Q.-M.; Huang, X.-Y. Organometallics
2000, 19, 960.
(9) Coucouvanis, D. Acc. Chem. Res. 1991, 24, 1.
(10) Darensbourg, M. Y.; Lyon, E. J.; Smee, J. J. Coord. Chem. ReV.
2000, 206, 533.
(16) Song, L.-C.; Guo, D.-S.; Hu, Q.-M; Su, F.-H.; Sun, J.; Huang, X.-
Y. J. Organomet. Chem. 2001, 622, 210.
(11) Song, L.-C. Acc. Chem. Res. 2005, 38, 21.
(17) Song, L.-C.; Zhu, W.-F.; Hu, Q.-M. Organometallics 2002, 21, 5066.
10.1021/om070020a CCC: $37.00 © 2007 American Chemical Society
Publication on Web 03/06/2007

µ-η1:η5-Ph2PC5H4 Ligand-Containing Dinuclear Complexes
Organometallics, Vol. 26, No. 8, 2007 1967
Scheme 1
Scheme 3
Scheme 2
showed three absorption bands in the range 2047-1893 cm-1
for their carbonyls attached to transition metals. In addition,
the 1H NMR spectra of 1 and 2 displayed three and four singlets
in the range 4.64-6.00 ppm for their monosubstituted cyclo-
pentadienyl rings.14,26 The 31P NMR spectra of 1 and 2 each
exhibited one singlet at 39.70 or 35.13 ppm for their P atoms
attached to cobalt atoms. It is worth pointing out that these two
singlets were broadened by the quadrupole effects of 59Co
nuclei27 to give a half-height width Wh/2 ) 1303 or 1208 Hz,
respectively.
In order to show the generality of this synthetic methodology
for preparation of such µ-η1:η5-Ph2PC5H4-containing transition-
metal clusters, we further carried out reactions of η5-Ph2-
PC5H4(CO)3MLi with another type of tetrahedral clusters, (µ3-
RC)Co3(CO)9 (R ) Me, Ph), under similar conditions. As a
result, the expected µ-η1:η5-Ph2PC5H4 ligand-containing cluster
complexes 3-6 were produced in 32-61% yields. Obviously,
the possible pathway for formation of 3-6 is similar to that
suggested for formation of 1 and 2, in which the corresponding
intermediates m3-m6 are first generated by the above-mentioned
intermolecular d9-ML3/d5-ML5 isolobal displacement, and then
the final products 3-6 can be produced by intramolecular
coordination of their P atoms to cobalt atoms followed by loss
of their CO ligands (Scheme 3).
Results and Discussion
Synthesis and Spectroscopic Characterization of the µ-η1:
η5-Ph2PC5H4-Containing Tetrahedral Clusters 1-6 and
Dinuclear Complex 8. We found that the η5-Ph2PC5H4-
containing isolobal reagents η5-Ph2PC5H4(CO)3MLi (M ) Mo,
W) prepared from M(CO)6 and diphenylphosphinocyclopenta-
dienyllithium could react in situ with tetrahedral cluster (µ3-
S)FeCo2(CO)9 in THF at about 60 °C to afford the µ-η1:η5-
Ph2PC5H4-containing tetrahedral cluster complexes 1 and 2 in
41% and 38% yields, respectively (Scheme 1).
So far, the mechanism for formation of 1 and 2 is not clear
to us. However, according to the previously reported similar
isolobal reactions14,15,18 and those well-documented transition-
metal-bound CO substitutions by heteroatom ligands,19-21 we
might suggest a possible pathway to account for the formation
of 1 and 2 (Scheme 2). As shown in Scheme 2, the reactions
would first give the intermediates m1 and m2 via the intermo-
lecular d9-ML3/d5-ML5 isolobal displacement of the Co(CO)3
fragment in (µ3-S)FeCo2(CO)9 by the η5-Ph2PC5H4M(CO)2
fragment generated from η5-Ph2PC5H4(CO)3MLi, and then the
intramolecular substitution of the cobalt-attached CO in m1 or
m2 by its P atom affords the final products 1 and 2. It is
interesting to note that 1 and 2 are actually the first transition-
metal tetrahedral cluster complexes containing a µ-η1:η5-Ph2-
PC5H4 ligand, although some homo- and heterodinuclear
complexes containing such a ligand were previously reported.22-25
Products 1 and 2 are air-stable solids, which have been
Products 3-6 are also air-stable solids and have been
1
characterized by elemental analysis and IR, H NMR, and 31P
1
NMR spectroscopy. In fact, the IR, H NMR, and 31P NMR
spectra of 3-6 are very similar to those displayed by 1 and 2.
For instance, the IR spectra of 3-6 also showed four absorption
bands around 2000 cm-1 for their carbonyls attached to
transition metals. The 1H NMR spectra of 3-6 exhibited three
and four singlets in the region 3.93-5.87 ppm for their
monosubstituted Cp rings.14,26 The 31P NMR spectra of 3-6
each displayed one broad singlet in the range 40-45 ppm with
a Wh/2 value in the region 84-168 Hz for their tertiary P atoms
coordinated to cobalt atoms.27 In addition, similar to 1 and 2,
the 31P chemical shifts of the Mo complexes 3 and 5 are greater
than those of the W complexes 4 and 6, implying the influence
of the transition metals directly attached to the µ-η1:η5-Ph2PC5H4
ligand.
characterized by elemental analysis and IR, H NMR, and 31P
NMR spectroscopy. For example, the IR spectra of 1 and 2
1
(18) Vahrenkamp, H. Comments Inorg. Chem. 1985, 4, 253.
(19) Song, L.-C.; Zeng, G.-H.; Hu, Q.-M.; Ge, J.-H.; Lou, S.-X.
Organometallics 2005, 24, 16.
(20) Seyferth, D.; Womack, G. B.; Song, L.-C.; Cowie, M.; Hames, B.
W. Organometallics 1983, 2, 928.
(21) Hogarth, G. J. Organomet. Chem. 2003, 672, 29.
(22) Casey, C. P.; Bullock, R. M.; Fultz, W. C.; Rheingold, A. L.
Organometallics 1982, 1, 1591.
(23) Duckworth, T. J.; Mays, M. J.; Conole, G.; McPartlin, M. J.
Organomet. Chem. 1992, 439, 327.
On the basis of synthesizing the µ-η1:η5-Ph2PC5H4-containing
tetrahedral (µ3-S)MFeCo and (µ3-RC)MCo2 cluster complexes
1-6, an attempt has been made to prepare the tetrahedral Mo2-
(24) Brumas, B.; de Caro, D.; Dahan, F.; de Montauzon, D.; Poilblanc,
R. Organometallics 1993, 12, 1503.
(25) Spadoni, L.; Sterzo, C. L.; Crescenzi, R.; Frachey, G. Organome-
tallics 1995, 14, 3149.
(26) Hart, W. P.; Rauch, M. D. J. Organomet. Chem. 1988, 355, 455.
(27) (a) Socol, S. M.; Lacelle, S.; Verkade, J. G. Inorg. Chem. 1987,
26, 3221. (b) Saito, T.; Sawada, S. Bull. Chem. Soc. Jpn. 1985, 58, 459.

1968 Organometallics, Vol. 26, No. 8, 2007
Song et al.
Scheme 4
Figure 1. Molecular structure of 1 with 30% probability level
ellipsoids.
Table 1. Selected Bond Lengths (Å) and Angles (deg) for
1-3 and 8
1
Mo(1)-S(1)
2.371(2)
2.730(2)
2.814(1)
54.51(5)
54.82(4)
75.96(4)
Co(1)-S(1)
2.198(2)
2.205(2)
2.197(2)
50.46(5)
104.45(5)
56.29(3)
Mo(1)-Co(1)
Co(1)-P(1)
Mo(1)-Fe(1)
Fe(1)-S(1)
S(1)-Fe(1)-Co(1)
S(1)-Fe(1)-Mo(1)
Fe(1)-S(1)-Mo(1)
S(1)-Mo(1)-Co(1)
S(1)-Co(1)-P(1)
S(1)-Co(1)-Mo(1)
2
3
W(1)-S(1)
2.357(2)
2.720(2)
2.792(2)
54.51(6)
54.83(6)
71.09(5)
Co(1)-P(1)
2.198(2)
2.556(2)
2.197(2)
50.74(6)
104.03(6)
56.06(4)
W(1)-Co(1)
Co(1)-Fe(1)
W(1)-Fe(1)
Fe(1)-S(1)
S(1)-Fe(1)-Co(1)
S(1)-Fe(1)-W(1)
Fe(1)-S(1)-Co(1)
S(1)-W(1)-Co(1)
P(1)-Co(1)-S(1)
S(1)-Co(1)-W(1)
Figure 2. Molecular structure of 2 with 30% probability level
ellipsoids.
Mo(1)-C(8)
Mo(1)-Co(1)
Mo(1)-Co(2)
Co(1)-Co(2)-Mo(1) 61.40(3)
C(10)-P(1)-Co(1)
C(8)-Mo(1)-Co(1)
2.120(5)
2.650(1)
2.695(1)
Co(1)-C(8)
Co(1)-P(1)
Co(1)-Co(2)
P(1)-Co(1)-Co(2)
1.918(6)
2.229(2)
2.483(1)
105.95(5)
of the P atom and the CO ligand present in the reaction system
with the two Mo atoms, respectively (Scheme 4).
101.82(2) Co(2)-Co(1)-Mo(1) 63.24(3)
X-ray Crystallography of 1-3 and 8. In order to unam-
biguously confirm the structures of tetrahedral clusters 1-6 and
dinuclear complex 8, we carried out the X-ray crystal diffraction
analyses of 1-3 and 8. Their selected bond lengths and angles
are listed in Table 1, while Figures 1-4 show their molecular
structures. As shown in Figures 1 and 2, clusters 1 and 2 indeed
contain a tetrahedral cluster core (µ3-S)MoFeCo or (µ3-S)-
WFeCo that bears seven carbonyls and an η1:η5-Ph2PC5H4
ligand bridged between Mo and Co or W and Co atoms. Among
the seven carbonyls attached to the metals, two carbonyls
attached to the Mo atom are semibridging and the others
terminal. For semibridging carbonyls Curtis’s definition is 0.1
e R ) (d2 - d1)/d2 e 0.6.28 For cluster 1, the calculated R
values of C(1)O(1) and C(2)O(2) attached to Mo are 0.41 and
0.37. For cluster 2, the calculated R values of C(1)O(1) and
C(2)O(2) attached to W are 0.32 and 0.37. So, they all fall into
the range of R values for semibridging carbonyls. The existence
of both terminal and semibridging CO’s confirmed by X-ray
diffraction analysis is consistent with the IR spectra of 1 and 2
described above. In fact, the overall geometry of 1 and 2 is
very similar to that of the known clusters Cp(µ3-S)MoFeCo-
(CO)7L and Cp(µ3-S)WFeCo(CO)7L (L ) MePrPhP).29
45.77(2)
Co(1)-C(8)-Mo(1)
81.9(2)
8
Mo(1)-Mo(2)
3.253(7)
1.932(2)
2.382(3)
76.95(9)
81.78(7)
116.01(6)
Mo(1)-P(1)
2.427(6)
1.821(2)
1.805(2)
107.00(6)
122.63(6)
36.26(7)
Mo(1)-C(1)
P(1)-C(12)
Mo(1)-C(18)
P(1)-C(23)
C(1)-Mo(1)-C(2)
C(1)-Mo(1)-P(1)
C(2)-Mo(1)-P(1)
C(23)-P(1)-Mo(1)
C(12)-P(1)-Mo(1)
C(24)-Mo(2)-C(23)
Co2 cluster complex (µ-η1:η5-Ph2PC5H4)CpMo2Co2(CO)9 (7) by
means of this synthetic method. However, it was found that
upon treatment of CpMoCo3(CO)11 with η5-Ph2PC5H4(CO)3-
MoLi in THF at 50-60 °C, the dinuclear complex (µ-η1:η5-
Ph2PC5H4)CpMo2(CO)5 (8) was unexpectedly obtained in 35%
yield, without any isolable 7 being observed. When 8 was fully
characterized by us using elemental analysis, 1H NMR and 31
P
NMR spectroscopy, and particularly X-ray crystallography, we
knew that 8 is a known complex.23 Up to now, we did not clearly
understand the mechanism of formation of 8. However, based
on the above-proposed pathways for formation of 1-6, it is
reasonable to suggest that 8 is most likely produced by loss of
its Co2(CO)5 from 7 or simply from m7 by loss of its Co2(CO)6
(presumably due to the strong steric repulsions between the two
bulky Cp and substituted Cp rings) followed by coordination
(28) Curtis, M. D.; Han, K. R.; Bulter, W. M. Inorg. Chem. 1980, 19,
2096.

µ-η1:η5-Ph2PC5H4 Ligand-Containing Dinuclear Complexes
Organometallics, Vol. 26, No. 8, 2007 1969
sponding values previously reported are 3.255(2) Å and 100.2-
(6)°,23 respectively.
Conclusion
We have developed a convenient “one-pot” synthetic route
that leads to the first µ-η1:η5-Ph2PC5H4 ligand-containing
tetrahedral cluster complexes 1-6 and the known dinuclear
complex 8. This route for production of 1-6 involves a d9-
ML3/d5-ML5 type of isolobal displacement reaction between
isolobal reagents η5-Ph2PC5H4(CO)3MLi (M ) Mo, W) and
tetrahedral cluster (µ3-S)FeCo2(CO)9, (µ3-MeC)Co3(CO)9, or
(µ3-PhC)Co3(CO)9 to give intermediates m1-m6, followed by
CO substitution of m1-m6 by heteroatom P of the Ph2P-
substituted Cp ring. This route leading to the unexpected
dinuclear complex 8 includes the isolobal displacement reaction
between isolobal reagent η5-Ph2PC5H4(CO)3MoLi and tetra-
herdal cluster CpMoCo3(CO)11 to give intermediates m7 and 7,
followed by extrusion of Co2(CO)6 or Co2(CO)5 and the P/CO
coordination with their two Mo atoms. It follows that both the
η5-Ph2PC5H4 ligand-containing isolobal reagents and the tetra-
hedral cluster substrates may exert great influence upon the
isolobal reactions to give different types of products.
Figure 3. Molecular structure of 3 with 30% probability level
ellipsoids.
Experimental Section
General Comments. All reactions were carried out under
prepurified nitrogen using standard Schlenk or vacuum-line tech-
niques. THF and diglyme were distilled from sodium/benzophenone
ketyl under nitrogen. M(CO)6 (M ) Mo, W) and Ph2PCl were
available from commercial suppliers without further purification.
CpNa,30 n-BuLi,31 Ph2PC5H4Li,32 (µ3-S)FeCo2(CO)9,33 (µ3-RC)Co3-
35
(CO)9 (R ) Me, Ph),34 and CpMoCo3(CO)11 were prepared by
slight modifications of the published procedures. Products were
separated by thin-layer chromatography on glass plates, 20 × 25
× 0.25 cm, coated with silica gel G (10-40 µm). IR spectra were
taken on a Bruker Vector 22 infrared spectrophotometer, 1H NMR
on a Bruker AC-P 200 MHz NMR or a Bruker 300 MHz NMR
spectrometer, and 31P NMR on a Bruker 300 MHz NMR or a Varian
Mercury Plus 400 MHz spectrometer. Elemental analyses were
performed on an Elementar Vario EL analyzer, and melting points
were determined on a Yanaco MP-500 apparatus, respectively.
Preparation of (µ-η1:η5-Ph2PC5H4)(µ3-S)MoFeCo(CO)7 (1). A
100 mL three-necked flask equipped with a magnetic stir-bar, two
serum caps, and a reflux condenser topped with a nitrogen inlet
tube was charged with a THF solution (20 mL) of CpNa (1.25
mmol), and then the solution was cooled to -78 °C by a dry ice/
acetone bath. To this cooled solution was added Ph2PCl (0.280 g,
1.25 mmol), and the mixture was warmed to room tempertature.
After the mixture was stirred at this temperature for 0.5 h, it was
cooled again to -78 °C, and then a hexane solution (0.70 mL) of
n-BuLi (1.20 mmol) was added. The mixture was warmed again
to room temperature and stirred at this temperature for 1 h to give
a THF solution of Ph2PC5H4Li (ca. 1.0 mmol). To this THF solution
Figure 4. Molecular structure of 8 with 30% probability level
ellipsoids.
Figure 3 demonstrates that cluster 3 is similar to 1 and 2,
which consists of a tetrahedral cluster core (µ3-MeC)MoCo2,
seven metal-bound carbonyls, and an η1:η5-Ph2PC5H4 ligand
bridged between Mo and Co atoms. However, among the seven
carbonyls, only one carbonyl, namely, C(1)O(1) (R ) 0.41), is
semibridging and the others terminal. In addition, the dihedral
angle between the substituted Cp ring and triangle plane C(8)-
Co(1)-Co(2) in 3 is 35.8(9)°, which is much smaller than that
(52.4(1)°) between the substituted Cp ring and triangle plane
Fe(1)-Co(1)-S(1) in its analogous cluster 1.
The crystal structure of 8 as shown in Figure 4 is composed
of an η1:η5-Ph2PC5H4 ligand bridged between the two molyb-
denum atoms; in addition, Mo(2) is coordinated by three
carbonyls and Mo(1) by two carbonyls and a Cp ring. Actually,
all the geometric parameters of our complex are nearly the same
as those previously reported for this complex. For example, the
metal-metal Mo(1)-Mo(2) bond length and the bond angle
between the two cis carbonyls C(3)-Mo(2)-C(5) in our
complex are 3.253(7) Å and 100.17(9)°, whereas the corre-
(30) Herrmann, W. A., Salzer, A. Eds. Synthetic Methods of Organo-
metallic and Inorganic Chemistry; G. Thieme Verlag: Stuttgart, 1996; Vol.
1, p 51.
(31) Jones, R. G.; Gilman, H. Organic Reactions; John Wiley & Sons,
Inc.: New York, 1951; Vol. 6, p 352.
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erscheid, P. Organometallics 2000, 19, 3818.
(33) Cowie, M.; Dekock, R. L.; Wagenmaker, T. R.; Seyferth, D.;
Henderson, R. S.; Gallagher, M. K. Organometallics 1989, 8, 119.
(34) Seyferth, D.; Hallgren, J. E.; Hung, P. L. K. J. Organomet. Chem.
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1970 Organometallics, Vol. 26, No. 8, 2007
Table 2. Crystal Data and Structural Refinements Details for 1-3 and 8
Song et al.
1
2
3
8
mol formula
mol wt
temp/K
cryst syst
space group
a/Å
C24H14CoFeMoO7PS‚0.25CH3C6H5
C24H14CoFeWO7PS‚0.25CH3C6H5
C26H17Co2MoO7P
686.17
C27H19Mo2O5P
646.27
711.14
799.05
298(2)
triclinic
P1h
293(2)
triclinic
P1h
293(2)
293(2)
monoclinic
P2(1)/c
10.457(3)
14.716(4)
17.430(4)
90
monoclinic
P2(1)/c
8.097(2)
17.001(4)
18.226(4)
90
10.485(6)
12.409(7)
12.774(7)
67.847(9)
65.925(8)
87.486(1)
1393.5(1)
2
10.485(7)
12.428(8)
12.748(9)
68.295(1)
65.845(1)
87.589(1)
1391.8(2)
2
b/Å
c/Å
R/deg
â/deg
101.293(4)
90
100.351(3)
90
γ/deg
V/Å3
2630.3(1)
4
2473.7(1)
4
Z
Dc/g cm-3
abs coeff/mm-1
F(000)
1.695
1.907
1.733
1.735
1.719
5.399
1.820
1.115
705
769
1360
1280
limiting indices
-12 e h e 8
-12 e k e 14
-14 e l e 15
5613
-6 e h e 12
-14 e k e 14
-15 e l e 15
5735
-11 e h e 12
-17 e k e 17
-20 e l e 15
13 511
-10 e h e 10
-22 e k e 21
-24 e l e 12
16 476
no.of rflns
no. of indep rflns
4728
50.00
4827
50.00
4638
50.02
5927
55.94
2θmax/deg
R
Rw
0.0352
0.0295
0.0350
0.0223
0.0860
0.0589
0.0663
0.0563
gooodness of fit
1.007
1.009
1.094
1.051
largest diff peak and hole/e Å-3
0.977/-0.413
0.690/-0.587
0.497/-0.409
0.345/-0.408
of η5-Ph2PC5H4Li was added Mo(CO)6 (0.264 g, 1.0 mmol). The
mixture was stirred at reflux for 16 h to give a red solution of
η5-Ph2PC5H4(CO)3MoLi. To this solution was added (µ3-S)FeCo2-
(CO)9 (0.456 g, 1.0 mmol), and the mixture was stirred at about
60 °C for an additional 1 h. Solvent was removed under reduced
pressure, and the residue was extracted with CH2Cl2. The extracts
were subjected to TLC separation. Elution with CH2Cl2/petroleum
ether (2:1 v/v) produced a red-brown band, from which 0.284 g
(41%) of 1 as a brown-red solid was obtained, mp 110-112 °C.
Anal. Calcd for C24H14CoFeMoO7PS: C, 41.89; H, 2.05. Found:
C, 42.20; H, 1.68. IR (KBr disk): νC≡O, 2047 (s), 1992 (vs), 1904
Co3(CO)9 (0.456 g, 1.0 mmol) was used instead of (µ3-S)FeCo2-
(CO)9, and the mixture of (µ3-MeC)Co3(CO)9 with η5-Ph2-
PC5H4(CO)3WLi was stirred at 60 °C for 6 h. A 0.469 g (61%)
amount of 4 as a brown-green solid was obtained, mp 180 °C (dec).
Anal. Calcd for C26H17Co2O7PW: C, 40.34; H, 2.21. Found: C,
40.38; H, 2.20. IR (KBr disk): νC≡O, 2042 (s), 1993 (vs), 1975
1
(vs), 1926 (s) cm-1. H NMR (300 MHz, CDCl3): 3.71 (s, 3H,
CH3), 4.19, 5.08 (2s, 2H, H3, H4), 5.54, 5.69 (2s, 2H, H2, H5), 7.44-
7.87 (m, 10H, 2C6H5). 31P NMR (121 MHz, CDCl3, 85% H3PO4):
40.83 (br s, Wh/2 ) 84 Hz) ppm.
Preparation of (µ-η1:η5-Ph2PC5H4)(µ3-PhC)MoCo2(CO)7 (5).
The same procedure as for 1 was followed, except that (µ3-PhC)-
Co3(CO)9 (0.518 g, 1.0 mmol) was employed in place of (µ3-S)-
FeCo2(CO)9, and the mixture of (µ3-PhC)Co3(CO)9 with η5-
Ph2PC5H4(CO)3MoLi was stirred at 60 °C for 2.5 h. A 0.245 g
(33%) amount of 5 as a brown-green solid was obtained, mp 200
°C (dec). Anal. Calcd for C31H19Co2MoO7P: C, 49.76; H, 2.56.
Found: C, 49.73; H, 2.77. IR (KBr disk): νC≡O, 2064 (s), 2007
(vs), 1980 (vs), 1904 (m) cm-1. 1H NMR (300 MHz, CDCl3): 3.93,
5.01 (2s, 2H, H3, H4), 5.54, 5.84 (2s, 2H, H2, H5), 7.01-7.89 (m,
15H, 3C6H5) ppm. 31P NMR (121 MHz, CDCl3, 85% H3PO4):
44.07 (br s, Wh/2 ) 168 Hz) ppm.
1
(s) cm-1. H NMR (200 MHz, CDCl3): 4.64, 4.74 (2s, 2H, H3,
H4), 5.43, 5.80 (2s, 2H, H2, H5), 7.45-7.98 (m, 10H, 2C6H5) ppm.
31P NMR (121 MHz, CDCl3, 85% H3PO4): 39.70 (br s, Wh/2
1303 Hz) ppm.
)
Preparation of (µ-η1:η5-Ph2PC5H4)(µ3-S)WFeCo(CO)7 (2). The
same THF solution of Ph2PC5H4Li as prepared by the procedure
described in the preparation of 1 was evaporated to dryness at
reduced pressure, and then the residue was redissolved in diglyme
(20 mL). To this diglyme solution was added W(CO)6 (0.352 g,
1.0 mmol), and the mixture was stirred and refluxed for 6 h to
give a red solution of η5-Ph2PC5H4(CO)3WLi. After diglyme was
removed at reduced pressure, THF (20 mL) and (µ3-S)FeCo2(CO)9
(0.456 g, 1.0 mmol) were added. The new mixture was stirred at
about 60 °C for another 1 h. The same workup as that for 1 afforded
0.294 g (38%) of 2 as a brown-red solid, mp 126-128 °C. Anal.
Calcd for C24H14CoFeO7PSW: C, 37.15; H, 1.82. Found: C, 37.17;
Preparation of (µ-η1:η5-Ph2PC5H4)(µ3-PhC)WCo2(CO)7 (6).
The same procedure as for 2 was followed, but (µ3-PhC)Co3(CO)9
(0.518 g, 1.0 mmol) was utilized in place of (µ3-S)FeCo2(CO)9. A
0.270 g (32%) amount of 6 as a brown-green solid was obtained,
mp 200 °C (dec). Anal. Calcd for C31H19Co2O7PW: C, 44.53; H,
2.29. Found: C, 44.41; H, 2.33. IR (KBr): νC≡O, 2051 (s), 2003
(vs), 1980 (vs), 1895 (s) cm-1. 1H NMR (300 MHz, CDCl3): 4.09,
5.08 (2s, 2H, H3, H4), 5.47, 5.87 (2s, 2H, H2, H5), 7.01-7.87 (m,
15H, 3C6H5) ppm. 31P NMR (121 MHz, CDCl3, 85% H3PO4):
40.42 (br s, Wh/2 ) 149 Hz) ppm.
H, 1.95. IR (KBr disk): νC≡O, 2046 (s), 1981 (vs), 1893 (s) cm-1
.
1H NMR (200 MHz, CDCl3): 5.02 (s, 2H, H3, H4), 5.54, 6.00 (2s,
2H, H2, H5), 7.65-8.20 (m, 10H, 2C6H5) ppm. 31P NMR (161 MHz,
CDCl3, 85% H3PO4): 35.13 (br s, Wh/2 ) 1208 Hz) ppm.
Preparation of (µ-η1:η5-Ph2PC5H4)(µ3-MeC)MoCo2(CO)7 (3).
The same procedure as for 1 was followed, but (µ3-MeC)Co3(CO)9
(0.456 g, 1.0 mmol) was used instead of (µ3-S)FeCo2(CO)9. A 0.334
g (50%) amount of 3 as a brown-green solid was obtained, mp
179 °C (dec). Anal. Calcd for C26H17Co2MoO7P: C, 45.51; H, 2.50.
Found: C, 45.33; H, 2.58. IR (KBr disk): νC≡O, 2042 (s), 1993
(vs), 1976 (vs), 1932 (s) cm-1. 1H NMR (300 MHz, CDCl3): 3.74
(s, 3H, CH3), 4.04, 5.03 (2s, 2H, H3, H4), 5.64 (s, 2H, H2, H5),
7.43-7.92 (m, 10H, 2C6H5) ppm. 31P NMR (121 MHz, CDCl3,
85% H3PO4): 44.47 (br s, Wh/2 ) 93 Hz) ppm.
Unexpected Formation of (µ-η1:η5-Ph2PC5H4)CpMo2(CO)5
(8). The same procedure as for 1 was followed, except that
CpMoCo3(CO)11 (0.730 g, 1.0 mmol) was used instead of (µ3-S)-
FeCo2(CO)9, and the new mixture was stirred at 50 °C for 2 h and
at 60 °C for 1 h. A 0.228 g (35%) amount of 8 as a brown solid
was obtained, mp 182 °C (dec). Anal. Calcd for C27H19Mo2O5P:
C, 50.18; H, 2.96. Found: C, 50.15; H, 2.90. IR (KBr): νC≡O, 1975
1
(vs), 1915 (vs), 1870 (vs), 1842 (s) cm-1. H NMR (300 MHz,
CDCl3): 3.20, 4.46 (2s, 2H, H3, H4), 4.96 (s, 5H, C5H5), 5.28, 5.50
(2s, 2H, H2, H5), 7.30-7.70 (m, 10H, 2C6H5) ppm. 31P NMR (121
MHz, CDCl3, 85% H3PO4): 63.40 (s) ppm. This 31P NMR chemical
Preparation of (µ-η1:η5-Ph2PC5H4)(µ3-MeC)WCo2(CO)7 (4).
The same procedure as for 2 was followed, except that (µ3-MeC)-

µ-η1:η5-Ph2PC5H4 Ligand-Containing Dinuclear Complexes
Organometallics, Vol. 26, No. 8, 2007 1971
shift is relative to 85% H3PO4, which corresponds to -78.40 ppm
relative to P(OMe)3 (very close to that reported, -78.7 ppm),23
since the 31P NMR chemical shift of P(OMe)3 is 141.8 ppm relative
to 85% H3PO4.36
97 program38 and refined by full-matrix least-squares techniques
(SHELXL-97)39 on F2. Hydrogen atoms were located by using the
geometric method. Details of crystal data, data collections, and
structure refinements are summarized in Table 2.
Crystal Structure Determinations of 1-3 and 8. Single crystals
of 1 and 2 suitable for X-ray diffraction analyses were obtained by
slow diffusion of toluene into their CH2Cl2 solutions at room
temperature, while the X-ray-quality crystals of 3 and 8 were grown
by slow diffusion of petroleum ether into their CH2Cl2 solutions at
4 °C, respectively. A single crystal of 1, 2, 3, or 8 was mounted on
a Bruker SMART 1000 automated diffractometer. Data were
collected at room temperature, using a graphite monochromator with
Mo KR radiation (λ ) 0.71073 Å) in the ω-φ scanning mode.
Absorption correction was performed by the SADABS program.37
The structures were solved by direct methods using the SHELXS-
Acknowledgment. We are grateful to the National Natural
Science Foundation of China for financial support of this work.
Supporting Information Available: Full tables of crystal data,
atomic coordinates, thermal parameters, and bond lengths and angles
for 1-3 and 8 as CIF files. This material is available free of charge
via the Internet at http://pubs.acs.org.
OM070020A
(36) Attanasi, O. A.; Baccolini, G.; Boga, C.; De Crescentini, L.;
Filippone, P.; Mantellini, F. J. Org. Chem. 2005, 70, 4033.
(37) Sheldrick, G. M. SADABS, A Program for Empirical Absorption
Correction of Area Detector Data; University of Go¨ttingen: Germany, 1996.
(38) Sheldrick, G. M. SHELXS97, A Program for Crystal Structure
Solution; University of Go¨ttingen: Germany, 1997.
(39) Sheldrick, G. M. SHELXL97, A Program for Crystal Structure
Refinement; University of Go¨ttingen: Germany, 1997.