C60-induced alkyne cycloaddition with W(CO)(PhC≡CPh) 3

Article abstract of DOI:10.1021/om3006933

Reaction of C₆₀ and W(CO)(PhC≡CPh)₃ in refluxing o-dichlorobenzene affords the fullerene complexes W(CO)( η²-C₂Ph₂)(η²-C ₆₀)(η⁴-C₄Ph₄) (4) and W(

Full text of DOI:10.1021/om3006933

Article
pubs.acs.org/Organometallics
C60-Induced Alkyne Cycloaddition with W(CO)(PhCCPh)3
Shu-Jou Wang and Wen-Yann Yeh*
Department of Chemistry, National Sun Yat-Sen University, Kaohsiung 804, Taiwan
S
* Supporting Information
ABSTRACT: Reaction of C60 and W(CO)(PhCCPh)3 in
refluxing o-dichlorobenzene affords the fullerene complexes
W(CO)(η2-C2Ph2)(η2-C60)(η4-C4Ph4) (4) and W(CPh)-
(CO)(η2-C60)(η5-C5Ph5) (5) and the η3-benzyl complex
W(CO)2(η5:η3-C5Ph4(o-C6H4)CHPh) (6). The carbocylic
groups in these compounds are arising from [2 + 2] and [2
+ 2 + 1] cycloaddition of the diphenylacetylene ligands, likely
induced by coordination of the bulky C60 molecule. The
structures of 4 and 6 have been determined by an X-ray
diffraction study.
ne of the most fascinating aspects pertaining to
Oorganometallic chemists concerns the C−H bond
activation and C−C bond formation of organic substrates at
transition-metal centers,1 because these processes hold the
promise of leading to efficient and catalytic methods for the
selective conversion of hydrocarbon feedstocks into function-
alized organic compounds.2 For instance, reactions of metal
carbonyls with alkyne derivatives are known to give a wide
variety of metallacyclic and carbocyclic products.3 Recently, the
availability of gram quantities of the fullerene C60 has facilitated
the study of the reactivity of this intriguing molecule.4,5
Subsequent work has been extensive, and many attempts have
been made to coordinate fullerenes to metals6 and to
incorporate metal-binding groups into their frameworks.7
Investigation of the influence of coordinated fullerenes on the
reactivity and structure of the metal complexes also becomes an
attractive research topic.8 We recently described the reaction of
C60 and W(NCMe)(PhCCPh)3 leading to alkyne−alkyne
coupling to generate 1 and 2 (Scheme 1),9 and subsequent
thermal reaction of 2 proceeded with interesting C−H bond
activation and C−C bond formation to give 3.10 Herein we
present quite different results from the reaction of C60 with the
carbonyl complex W(CO)(PhCCPh)3.
RESULTS AND DISCUSSION
■
Though W(NCMe)(PhCCPh)3 reacted quickly with C60 in
refluxing chlorobenzene (130 °C),9 no reaction occurred
between W(CO)(PhCCPh)3 and C60 at this temperature.
It appears that the W(CO)(RCCR′)3 stoichiometry is
particularly stable, as suggested by theoretical analyses11 and
several reactivity studies.12 Under harsher conditions (refluxing
o-dichlorobenzene at 180 °C), however, the reaction proceeded
to generate the two new tungsten−fullerene complexes
W(CO)(η2-C2Ph2)(η2-C60)(η4-C4Ph4) (4) and W(CPh)-
(CO)(η2-C60)(η5-C5Ph5) (5) and the η3-benzyl complex
W(CO)2(η5:η3-C5Ph4(o-C6H4)CHPh) (6) (see Scheme 2)
after separation by TLC (silica gel) and HPLC (5PYE
column). Although compound 6 contains no C60, it is not
obtainable by heating W(CO)(PhCCPh)3 alone and is most
likely derived from the thermal reaction of 5.
Compound 4 forms an air-stable, green solid. The molecular
ion peak at m/z 1466 is the combination of W(CO)(C2Ph2)3
and one C60 moiety, while the CO stretching frequency at 2023
cm−1 is red-shifted 24 cm−1 in comparison to W(CO)(PhC
CPh)3 (2047 cm−1). The molecular structure of 4 is illustrated
in Figure 1. It consists of discrete molecules with each tungsten
atom bonded to one terminal CO (W1−C1−O1 = 178(1)°),
one diphenylacetylene, one tetraphenylcyclobutadiene, and one
C
60 moiety. Taking the centers of the cyclobutadiene, the C2−
Scheme 1
C9 bond, and the C44−C45 bond, the coordination about the
tungsten atom can be described as a distorted tetrahedron. The
organic ligands are essentially in an eclipsed form with respect
to the W1−C1−O1 axis, as is evidenced by their torsional
angles. Apparently, the coordinated CO is sterically forcing the
organic ligands from being parallel, where C2−C9 is tilted from
the W1−C1−O1 vector by 9.2°, C44−C45 by 2.9°, C23−C16
by 5.7°, and C30−C37 by 14.5°. These give rise to small
differences between the upper and lower W−C distances, such
Received: July 23, 2012
Published: August 21, 2012
© 2012 American Chemical Society
6491
dx.doi.org/10.1021/om3006933 | Organometallics 2012, 31, 6491−6495

Organometallics
Article
Scheme 2
significantly shorter than the lower W−C distances by 0.18 and
0.12 Å. The phenyl groups are bent away from the C4 plane by
angles ranging from 11° for C38 to 29° for C24; this reflects a
greater CO steric influence on the phenyl groups in the syn
position. The cyclobutadiene C−C distances, ranging from
1.44(1) to 1.49(1) Å, closely resemble those found for other
cyclobutadiene−metal complexes.13 The C60 molecule is linked
to the tungsten atom in an η2 fashion through a 6:6 ring
junction. The distance C44−C45 = 1.49(1) Å is elongated (ca.
0.11 Å) in comparison with other unperturbed 6:6 double
bonds and may be attributed to π-back-donation from the
tungsten atom.
Since terminal CO, η2-C60, and η4-C4Ph4 are normally
considered as two-, two-, and four-electron donors, the
remaining η2-C2Ph2 ligand in 4 must supply four electrons,
presumably from the filled π(⊥) and π(∥) orbitals, to the
tungsten atom to satisfy the 18-electron rule. The results are
reflected in the long C2C9 bond distance (1.31(1) Å) and
13C resonances at δ 192.5 and 174.3, consistent with those
measured for 4e-donating alkyne complexes.14 The η2-C60
carbons give rise to two 13C resonances at δ 77.3 and 77.0,
while the cyclobutadiene carbons present a sharp signal at δ
84.1, suggesting that the C4 ligand is fluxional with facile ring
rotation.
Compound 5 forms an air-stable, green solid. It is isomeric
with 4, with the ESI mass spectrum showing the molecular ion
peaks around m/z 1467. The IR spectrum displays a terminal
carbonyl absorption at 1997 cm−1, which is 26 cm−1 red-shifted
from the signal for 4. In contrast, the 13C{1H} NMR spectrum
of 5 displays a far downfield resonance at δ 304.9 to indicate
the presence of a tungsten−carbon multiple bond and a sharp
signal at δ 118.1 corresponding to an η5-C5Ph5 ligand. Since the
1H and 13C NMR spectra of 5 bear a close resemblance to
those of 2, a similar coordination environment for the tungsten
atom of 5 and 2 is anticipated. Presumably, the tungsten atom
of 5 is bonded to a terminal CO, an η5-C5Ph5, a CPh
(benzylidyne), and an η2-C60 ligand. Because of the chirality at
the pseudotetrahedral tungsten center, the single resonance at δ
Figure 1. Molecular structure of 4·CS2·C6H6 with 30% probability
ellipsoids. The solvents of crystallization and hydrogen atoms have
been artificially omitted. The tungsten atom is disordered at two sites,
and the ORTEP displays the W1 atom with 96% occupancy. Selected
bond distances (Å): W1−C1 = 2.03(1), W1−C2 = 2.060(9), W1−C9
= 2.013(9), W1−C16 = 2.344(9), W1−C23 = 2.165(9), W1−C30 =
2.306(9), W1−C37 = 2.421(9), W1−C44 = 2.282(9), W1−C45 =
2.264(9), C1−O1 = 1.11(1), C2−C9 = 1.31(1), C16−C23 = 1.48(1),
C16−C37 = 1.44(1), C23−C30 = 1.49(1), C30−C37 = 1.47(1),
C44−C45 = 1.49(1). Selected bond angles (deg): W1−C1−O1 =
178(1), C1−W1−C2 = 78.7(4), C1−W1−C9 = 116.0(4), C1−W1−
C16 = 121.3(4), C1−W1−C23 = 84.2(4), C1−W1−C30 = 91.0(4),
C1−W1−C37 = 126.8(4), C1−W1−C44 = 73.3(3), C1−W1−C45 =
111.5(4), C3−C2−C9 = 141.6(9), C2−C9−C10 = 140.2(8), C23−
C16−C37 = 90.0(7), C16−C23−C30 = 89.5(7), C23−C30−C37 =
88.8(7), C16−C37−C30 = 91.6(7).
that W1−C2 = 2.060(9) Å, W1−C9 = 2.013(9) Å, W1−C44 =
2.282(9) Å, and W1−C45 = 2.264(9) Å. The cyclobutadiene
ring is slightly deviated from planar ( 0.05 Å) and is bonded to
the tungsten atom asymmetrically, with W1−C23 = 2.165(9)
Å, W1−C16 = 2.344(9) Å, W1−C30 = 2.306(9) Å, and W1−
C37 = 2.421(9) Å, of which the upper W−C distances are
6492
dx.doi.org/10.1021/om3006933 | Organometallics 2012, 31, 6491−6495

Organometallics
Article
118.1 for the cyclopentadienyl carbons supports a dynamic
process with a facial Cp ring rotation. Interestingly, only one
broad resonance at δ 90.8 is observed for the two coordinated
fullerene carbons of 5, while two signals are recorded for 2 and
4. This suggests a lower energy barrier for the W−C60 bond
rotation of 5, giving rise to a total of 30 13C signals for the C60
carbons.
Compound 6 forms an air-stable, orange-red solid. The FAB
mass spectrum shows the molecular ion peak at m/z 774,
corresponding to addition of one CO ligand to W(CO)-
(C2Ph2)3. This is consistent with the observation of two
terminal CO stretchings at 1949 and 1872 cm−1 for 6. Crystals
of 6 suitable for an X-ray diffraction study were grown from
CH2Cl2/MeOH at ambient temperature. An ORTEP diagram
is depicted in Figure 2, and the configuration surrounding the
Figure 3. Highlighted configuration of 6 with selected bond distances
1
(Å). The H and 13C resonances for the allyl group are indicated.
C32, and C41 are 0.08−0.30 Å above the Cp plane, while the
C17 atom is bent downward by 0.18 Å, likely due to steric
constraints of the benzyl moiety.
1
The H and 13C{1H} NMR spectra of 6 are complicated,
where the resonances for the η3-allyl groups are assigned,
shown in Figure 3, on the basis of an H,H-COSY and a 2D-
HSQC experiments. The benzyl proton resonance at δ 5.51 and
the ortho proton resonance at δ 4.05 are significantly shielded in
comparison to other ring proton resonances (δ 7.84−6.77),
suggesting an anionic character for the η3-allyl segment and/or
the anisotropic shielding effects of the numerous close aromatic
groups. The C1 symmetry of 6 gives rise to two carbonyl carbon
resonances at δ 235.0 and 231.0 and five cyclopentadienyl ring
carbon resonances at δ 123.6, 115.6, 111.9, 110.8, and 110.2.
The cyclobutadiene complex W(CO)(η2-C2Ph2)2(η4-C4Ph4)
was previously prepared by heating W(CO)(PhCCPh)3 in
molten diphenylacetylene at 120 °C.12c Compound 4 is formed
through a similar [2 + 2] cycloaddition of the diphenylacetylene
ligands, likely induced by coordination of the bulky C60
molecule. Alternatively, a [2 + 2 + 1] cycloaddition pathway
would yield a C5Ph5 and a benzylidyne moiety to give 5,
analogous to the formation of 2.15 Transformation from 5 to 6
appears involving several ligand activation and migration
processes. A plausible reaction sequence is depicted in Scheme
2. First, the intermediate I is produced, resembling the
formation of 3 from 2, through a phenyl ortho C−H bond
activation and C−C bond coupling with the benzylidyne ligand.
Subsequent conversion from I to II is compatible with the
protonation of Rh(PPri3)(η5-Cp)(CPh2) to produce the η3-
benzyl complex [Rh(PPri3)(η5-Cp)(η3-CHPh2)]+ described by
Werner and co-workers.16 Finally, the coordinated C60 is
replaced by a carbonyl due to steric congestion. Nevertheless,
an alternative pathway initiated by C60/CO exchange cannot be
excluded. Since thermolysis of 5 or heating a mixture of 4 and 5
in o-dichlorobenzene solution did not generate 6, the incoming
carbonyl ligand likely came from decomposition of the
reactants. Supporting this, cothermolysis of 5 and W(CO)-
(PhCCPh)3 (5 equiv) in refluxing o-dichlorobenzene was
found to produce 6 in 66% yield.
Figure 2. Molecular structure of 6 with 30% probability ellipsoids. The
hydrogen atoms have been artificially omitted. Selected bond distances
(Å): W1−C1 = 1.94(1), W1−C2 = 1.92(2), W1−C5 = 2.44(2), W1−
C10 = 2.41(2), W1−C11 = 2.28(1), W1−C18 = 2.30(1), W1−C19 =
2.29(1), W1−C26 = 2.31(1), W1−C33 = 2.37(1), W1−C40 =
2.39(1), C1−O1 = 1.15(1), C2−O2 = 1.19(2), C17−C18 = 1.49(1),
C18−C19 = 1.44(2), C18−C40 = 1.42(1), C19−C26 = 1.43(1),
C26−C33 = 1.44(2), C33−C40 = 1.45(1). Selected bond angles
(deg): W1−C1−O1 = 175(1), W1−C2−O2 = 178(1), W1−C5−C6
= 122(1), W1−C5−C10 = 73(1), W1−C10−C5 = 76(1), W1−C10−
C9 = 120(1), W1−C10−C11 = 67.4(9), W1−C11−C10 = 78(1),
W1−C11−C12 = 110.9(9), C6−C5−C10 = 119(2), C5−C10−C11 =
115(2), C9−C10−C11 = 121(2), C10−C11−C12 = 126(2).
tungsten atom is highlighted in Figure 3. The tungsten atom is
linked to two terminal carbonyls, an η3-benzyl, and an η5-C5Ph5
group, giving an 18-electron count for the complex. The
cyclopentadienyl ring is coordinated to the tungsten atom
asymmetrically, with the W−C bond lengths varying from
2.28(1) through 2.39(1) Å. It is interesting that the ortho C−H
bond of one phenyl group is activated and coupled with the
benzylidyne ligand to generate an η3-benzyl species, where the
tungsten atom formally forms a σ bond to the benzylic carbon
(W1−C11 = 2.28(1) Å) and a π bond to the ipso and ortho
carbons of the arene ring, with W1−C5 = 2.44(2) Å and W1−
C10 = 2.41(2) Å. The C11 atom is 0.18(1) Å away from the
arene plane, and the dihedral angle between the C5−C10−C9
plane and the C10−C11−C12 plane is 44(3)°. The C−C
bonds within the benzyl ring are localized, varying from 1.32(2)
to 1.49(2) Å. Noticeably, the phenyl ipso carbons C20, C27,
In summary, we have demonstrated C60-induced alkyne
cyclization and scission reactions with W(CO)(PhCCPh)3
to give complexes containing η4-C4Ph4, η5-C5Ph5, η3-benzyl,
6493
dx.doi.org/10.1021/om3006933 | Organometallics 2012, 31, 6491−6495

Organometallics
Article
suitable for X-ray analysis were each mounted in a thin-walled glass
capillary and aligned on the Nonius Kappa CCD diffractometer, with
graphite-monochromated Mo Kα radiation (λ = 0.710 73 Å). The θ
range for data collection is 1.34−25.11° for 4·CS2·C6H6 and 1.64−
25.01° for 6. Of the 25 453 and 26 137 reflections collected, 11 069
and 11 333 reflections were independent for 4·CS2·C6H6 and 6,
respectively. All data were corrected for Lorentz and polarization
effects and for the effects of absorption. The structure was solved by
direct methods and refined by least-squares cycles. The non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were included but
not refined. All calculations were performed using the SHELXTL-97
package. The data collection and refinement parameters are presented
in Table 1.
and terminal benzylidyne ligands. The results are quite different
from those observed for W(NCMe)(PhCCPh)3, where the
acetonitrile ligand is able to insert into one 6:6 or 6:5 ring
junction of C60. We are currently investigating the reactions of
fullerene derivatives with other metal poly(alkyne) complexes.
EXPERIMENTAL SECTION
■
General Methods. All manipulations were carried out under an
atmosphere of purified dinitrogen with standard Schlenk techniques.
Solvents were dried over appropriate reagents under dinitrogen and
distilled immediately before use. W(CO)(PhCCPh)3 was prepared
as described in the literature.17 C60 (99%) was purchased from Bucky
USA. Preparative thin-layer chromatographic (TLC) plates were
prepared from silica gel (Merck). 1H and 13C spectra were obtained on
a Varian Unity INOVA-500 spectrometer at 500 and 125.7 MHz,
respectively. Fast-atom-bombardment (FAB) and electrospray ioniza-
tion (ESI) mass spectra were recorded on a JEOL JMS-700 HR and
Thermo Finnigan Triple Quadrupole mass spectrometer, respectively.
Reaction of C60 and W(CO)(PhCCPh)3. C60 (60 mg, 0.083
mmol) and W(CO)(PhCCPh)3 (123 mg, 0.165 mmol) were placed
in an oven-dried 50 mL Schlenk tube, equipped with a condenser,
under a dinitrogen atmosphere. o-Dichlorobenzene (10 mL) was
introduced into the flask via a syringe, and the solution was heated to
reflux for 7 min, resulting in a solution color change from purple to
deep brown. The tube was immediately put into an ice bath to cool
down the reaction mixture. The volatile materials were removed under
vacuum, and the residue was subjected to TLC, with carbon disulfide
as eluent. Isolation of the material forming the first purple band
recovered C60 (47 mg, 0.065 mmol). Isolation of the material forming
the second green band gave a mixture, which was further purified by
HPLC (5PYE column), with toluene/n-hexane (2/1 v/v) as eluent, to
afford W(CO)(η2-C2Ph2)(η2-C60)(η4-C4Ph4) (4; 3 mg, 0.002 mmol,
1.2%) and W(CPh)(CO)(η2-C60)(η5-C5Ph5) (5; 10 mg, 0.0068
mmol, 4.1%). Isolation of the material forming the orange-red band
gave W(CO)2(η5:η3-C5Ph4(o-C6H4)CHPh) (6; 7 mg, 0.009 mmol,
5.5%) (the yields are all based on the tungsten starting material used).
Characterization of 4. MS (ESI): m/z 1466 (M+, 184W). IR
Table 1. Crystallographic Data for 4·CS2·C6H6 and 6
4·CS2·C6H6
6
chem formula
cryst syst
fw
C110H36OS2W
triclinic
C44H30O2W
triclinic
1621.36
774.53
T, K
200(2)
200(2)
space group
a, Å
P1
P1
̅
̅
13.1225(6)
16.4596(8)
17.0700(8)
115.228(3)
96.147(3)
98.341(3)
3240.7(3)
2
12.575(3)
15.011(4)
18.114(4)
101.157(4)
90.189(4)
103.451(3)
3258(1)
4
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å3
Z
D
calcd, g cm−3
1.662
1.579
μ, mm−1
1.912
3.583
R1/wR2
GOF on F2
0.0696/0.1151
0.974
0.0676/0.1406
1.118
1
(methylcyclohexane, νCO): 2023 cm−1. H NMR (CD2Cl2, 25 °C): δ
ASSOCIATED CONTENT
* Supporting Information
CIF files giving X-ray crystal data for compounds 4·CS2·C6H6
and 6. This material is available free of charge via the Internet at
http://pubs.acs.org.
7.68−7.08 (m, Ph). 13C{1H} NMR (CD2Cl2, 25 °C): δ 212.9 (CO),
192.5, 174,3 (CC), 161.4, 158.5, 158.0, 155.4, 149.9, 147.9, 147.5,
147.2, 146.9, 146.6, 146.2, 145.9, 145.6, 145.5, 145.1, 145.0, 144.7,
144.6, 144.4, 144.0, 143.6, 143.4, 143.2, 143.1, 143.0, 142.7, 142.3,
142.2, 141.9, 141.8 (C60), 140.3, 138.8, 138.5, 137.2, 134.5, 133.9,
132.3, 130.6, 129.5, 129.0, 128.5, 128.4 (Ph), 84.1 (C4Ph4), 77.3, 77.0
(η2-C60).
■
S
AUTHOR INFORMATION
Notes
The authors declare no competing financial interest.
Characterization of 5. MS (ESI): m/z 1467 (M + H+, 184W).
HRMS (ESI): calcd for C103H31OW m/z 1467.1879, found m/z
1467.1876. IR (methylcyclohexane, νCO): 1997 cm−1. 1H NMR
(CD2Cl2, 25 °C): δ 7.45−7.01 (m, Ph). 13C{1H} NMR (CD2Cl2, 25
°C) δ 304.9 (WC), 216.4 (CO), 168.7, 164.1, 159.9, 148.5, 148.4,
147.9, 147.7, 147.6, 147.2, 146.5, 146.3, 146.0, 145.9, 145.8, 145.6,
145.4, 145.1, 145.0, 144.9, 144.7, 144.5, 143.9, 143.0, 142.9, 142.5,
142.4, 142.3, 141.8, 141.4 (C60), 133.4, 132.7, 132.3, 130.9, 129.0,
128.6, 128.4, 127.8 (Ph), 118.1 (C5Ph5), 90.8 (η2-C60).
■
ACKNOWLEDGMENTS
■
We are grateful for support of this work by the National
Science Council of Taiwan. We thank Mr. Ting-Shen Kuo
(National Taiwan Normal University, Taipei) for X-ray
diffraction analysis.
Characterization of 6. MS (FAB): m/z 774 (M+, 184W), 718 (M+
− 2CO). HRMS (FAB): calcd for C44H30O2W m/z 774.1755, found
m/z 774.1755. IR (n-hexane, νCO): 1949 (s), 1872 (s) cm−1. 1H NMR
(CD2Cl2, 25 °C): δ 7.84 (d, JH−H = 8 Hz, 1H, CHC6H5), 7.66 (d, JH−H
= 8 Hz, 2H, Ph), 7.32−7.00 (m, 22H, Ph, C6H4, CHC6H5), 6.89 (d,
JH−H = 8 Hz, 1H, C6H4), 6.81 (d, JH−H = 8 Hz, 1H, CHC6H5), 6.77 (t,
JH−H = 8 Hz, 1H, C6H4), 5.51 (s, 1H, CHC6H5), 4.05 (d, JH−H = 8 Hz,
1H, CHC6H5). 13C{1H} NMR (CD2Cl2, 25 °C): δ 235.0, 231.0 (CO),
154.1, 134.5, 134.3, 134.2, 134.0, 133.9, 133.8, 133.1, 133.0, 132.9,
132.7, 132.2, 128.8, 128.5, 128.3, 128.0, 127.8, 127.7, 127.6, 127.4,
126.6, 126.1 (Ph), 123.6, 115.6, 111.9, 110.8, 110.2 (Cp), 104.1, 75.2,
51.6 (allyl C).
REFERENCES
■
(1) (a) Ng, S. H. K.; Adams, C. S.; Hayton, T. W.; Legzdins, P.;
Patrick, B. O. J. Am. Chem. Soc. 2003, 125, 15210−15223. (b) Jones,
W. D. In Activation of Unreactive Bonds; Springer: Heidelberg,
Germany, 1999; pp 10−46. (c) Marks, T. J. Acc. Chem. Res. 1992,
25, 57−65. (d) Cordaro, J. G.; Bergman, R. G. J. Am. Chem. Soc. 2004,
126, 3432−3433. (d) Crabtree, R. H. The Organometallic Chemistry of
the Transition Metals; Wiley: Hoboken, NJ, 2009.
(2) (a) Crabtree, R. H. Dalton Trans. 2001, 2437−2538. (b) Labinger,
J. A.; Bercaw, J. E. Nature 2002, 417, 507−514. (c) Parshall, G. W.;
Ittel, S. D. Homogeneous Catalysis; Wiley: New York, 1992.
(3) (a) Omae, I. Appl. Organomet. Chem. 2008, 22, 149−166.
(b) Chiusoli, G. P.; Maitlis, P. M. Metal-Catalysis in Industrial Organic
Structure Determination for 4·CS2·C6H6 and 6. Compound 4
was crystallized from benzene/CS2/n-hexane and compound 6 from
CH2Cl2/MeOH at ambient temperature. Crystals of 4·CS2·C6H6 and 6
6494
dx.doi.org/10.1021/om3006933 | Organometallics 2012, 31, 6491−6495

Organometallics
Article
Processes; Royal Society of Chemistry: Colchester, U.K., 2006.
(c) Otsuka, S.; Nakamura, A. Adv. Organomet. Chem. 1976, 14,
245−283.
(4) (a) Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.;
Smalley, R. E. Nature 1985, 318, 162−163. (b) Kratschmer, W.; Lamb,
̈
L. D.; Fostiropoulos, K.; Huffman, D. R. Nature 1990, 347, 354−358.
(5) (a) Balch, A. L.; Olmstead, M. M. Chem. Rev. 1998, 98, 2123−
2165. (b) Hirsch, A.; Brettreich, M. Fullerenes; Wiley-VCH: Weinheim,
Germany, 2005. (c) Matsuo, Y.; Nakamura, E. Chem. Rev. 2008, 108,
3016−3028.
(6) (a) Fagan, P. J.; Calabrese, J. C.; Malone, B. Science 1991, 252,
1160−1161. (b) Koefod, R. S.; Hudgens, M. F.; Shapley, J. R. J. Am.
Chem. Soc. 1991, 113, 8957−8958. (c) Balch, A. L.; Catalano, V. J.;
Lee, J. W.; Olmstead, M. M. J. Am. Chem. Soc. 1992, 114, 5455−5457.
(d) Hsu, H.-F.; Shapley, J. R. J. Am. Chem. Soc. 1996, 118, 9192−9193.
(e) Lee, K.; Choi, Z.-H.; Cho, Y.-J.; Song, H.; Park, J. T.
Organometallics 2001, 20, 5564−5570. (f) Park, B. K.; Lee, G.; Kim,
K. H.; Kang, H.; Lee, C. Y.; Miah, M. A.; Jung, J.; Han, Y.-K.; Park, J.
T. J. Am. Chem. Soc. 2006, 128, 11160−11172. (g) Halim, M.;
Kennedy, R. D.; Khan, S. I.; Rubin, Y. Inorg. Chem. 2010, 49, 3974−
3976.
(7) (a) Taylor, R. Lecture Notes on Fullerene Chemistry; Imperial
College Press: London, 1999. (b) Thilgen, C.; Diederich, F. Chem. Rev.
2006, 106, 5049−5135. (c) Murata, M.; Murata, Y.; Komatsu, K.
Chem. Commun. 2008, 6083−6094. (d) Yeh, W.-Y.; Tsai, K.-Y.
Organometallics 2010, 29, 604−609. (e) Wu, Y.-Y.; Yeh, W.-Y.
Organometallics 2011, 30, 4792−4795. (f) Chen, C.-H.; Chen, C.-S.;
Dai, H.-F.; Yeh, W.-Y. Dalton Trans. 2012, 41, 3030−3037. (g) Martín,
N.; Altable, M.; Filippone, S.; Martín-Domenech, A. Synlett 2007,
3077−3095.
(8) Park, B. K.; Miah, M. A.; Lee, G.; Cho, Y.-J.; Lee, K.; Park, S.;
Choi, M.-G.; Park, J. T. Angew. Chem., Int. Ed. 2004, 43, 1712−1714.
(9) Yeh, W.-Y. Chem. Commun. 2011, 47, 1506−1508.
(10) Yeh, W.-Y. Angew. Chem., Int. Ed. 2011, 50, 12046−12049.
(11) (a) King, R. B. Inorg. Chem. 1968, 7, 1044−1046. (b) Wink, D.
J.; Creagan, T. Organometallics 1990, 9, 328−334.
(12) (a) Carriedo, G. A.; Howard, J. A. K.; Lewis, D. B.; Lewis, G. E.;
Stone, F. G. A. J. Chem. Soc., Dalton Trans. 1985, 905−912. (b) Okuda,
J.; Zimmermann, K. H. J. Organomet. Chem. 1990, 384, C21−24.
(c) Wink, D. J.; Cooper, N. J. Organometallics 1991, 10, 494−500.
(d) Yeh, W.-Y.; Liu, L.-K. J. Am. Chem. Soc. 1992, 114, 2267−2269.
(e) Yeh, W.-Y.; Peng, S.-M.; Lee, G.-H. J. Chem. Soc., Chem. Commun.
1993, 1056−1057. (f) Yeh, W.-Y.; Ho, C.-L.; Chiang, M. Y.; Chen., I.-
T. Organometallics 1997, 16, 2698−2708.
(13) (a) Dodge, R. P.; Schomaker, V. Acta Crystallogr. 1965, 18,
614−617. (b) Efraty, A.; Potenza, J. A.; Zyontz, L.; Daily, J.; Huang,
M. H. A.; Toby, B. J. Organomet. Chem. 1978, 145, 315−327.
(c) Chang, S.-C.; Yeh, W.-Y.; Lee, G.-H.; Peng, S.-M. J. Chin. Chem.
Soc. 2002, 49, 325−330.
(14) (a) Chisholm, M. H.; Clark, H. C.; Manzer, L. E.; Stothers, J. B.
J. Am. Chem. Soc. 1972, 94, 5087−5089. (b) Templeton, J. L.; Ward, B.
C. J. Am. Chem. Soc. 1980, 102, 3288−3290. (c) Templeton, J. L. Adv.
Organomet. Chem. 1989, 29, 1−100.
(15) (a) Filippou, A. C.; Volkl, C.; Grunleitner, W.; Kiprof, P. Angew.
̈
̈
Chem., Int. Ed. 1990, 29, 207−209. (b) Cairns, G. A.; Carr, N.; Green,
M.; Mahon, M. F. J. Chem. Soc., Chem. Commun. 1996, 2431−2432.
(16) Bleuel, E.; Schwab, P.; Laubender, M.; Werner, H. Dalton Trans.
2001, 266−273.
(17) (a) Tate, D. P.; Augl, J. M. J. Am. Chem. Soc. 1963, 85, 2174−
2175. (b) Baker, M. V.; North, M. R. J. Organomet. Chem. 1998, 565,
225−230.
6495
dx.doi.org/10.1021/om3006933 | Organometallics 2012, 31, 6491−6495