Complexation and activation of the bisfulleroid C64H4 with triosmium carbonyl clusters

Article abstract of DOI:10.1016/j.jorganchem.2012.05.034

Reaction of C₆₄H₄ (1) and Os₃(CO) ₁₀(NCMe)₂ in refluxing chlorobenzene affords (μ-H)Os₃(CO)₉(μ,η⁴-C ₆₄H₃) (2) and Os(CO)₃(η⁴-C ₆₄H₄) (3). Compound 2 apparently arises from C-H bond activation of 1 to generate an η⁴-dienyl motif. In contrast, compound 3 is produced by insertion of one osmium atom into a pentagonal ring of 1, together with the Os₃ cluster fragmentation. Complexes 2 and 3 have been characterized by IR, NMR, and mass spectroscopies. The structure of 3·C₇H₈ was determined by a single-crystal X-ray diffraction study.

Full text of DOI:10.1016/j.jorganchem.2012.05.034

Journal of Organometallic Chemistry 715 (2012) 69e72
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Complexation and activation of the bisfulleroid C64H4 with triosmium
carbonyl clusters
*
Shao-Tang Lien, Wen-Yann Yeh
Department of Chemistry, National Sun Yat-Sen University, Kaohsiung 804, Taiwan
a r t i c l e i n f o
a b s t r a c t
Reaction of C64H4 (1) and Os3(CO)10(NCMe)2 in refluxing chlorobenzene affords (m-H)Os3(CO)9(m, -
h4
Article history:
C64H3) (2) and Os(CO)3(
h
4-C64H4) (3). Compound 2 apparently arises from CeH bond activation of 1 to
Received 7 March 2012
Received in revised form
19 May 2012
generate an
h
4-dienyl motif. In contrast, compound 3 is produced by insertion of one osmium atom into
a pentagonal ring of 1, together with the Os3 cluster fragmentation. Complexes 2 and 3 have been
characterized by IR, NMR, and mass spectroscopies. The structure of 3$C7H8 was determined by a single-
crystal X-ray diffraction study.
Accepted 24 May 2012
Keywords:
Ó 2012 Elsevier B.V. All rights reserved.
CeH bond activation of C64H4
CeC activation bond of C64H4
Osmium carbonyl cluster
Osmium fullerene complex
Cluster fragmentation
1. Introduction
2. Results and discussion
Attachment of organometallic complexes to fullerenes is an
important area within fullerene chemistry, due to its potential
application in biological, magnetic, electronic, catalytic and optical
devices [1e10]. Meanwhile, preparation of endohedral
metalefullerene complexes (with metals inside the fullerene cage) in
isolable and stable form remains great challenges [11e14]. Traditional
metal/graphite laser and arc evaporation methods are limited in the
fullerene size and low product yield [15e20], while an alternative
approach by opening a temporary hole within a fullerene framework
[21e24], followed by metal complexation and insertion, might
provide a promising pathway. Rubin and coworkers have discovered
a versatile method leading to the bisfulleroid C64H4 (1) [25], which
contains an open cyclooctatriene ring accessible to metal binding. In
ourcontinuinginterest in metalefullerene chemistry[26e28], herein
we present the complexation and activation reactions of 1 with tri-
osmium carbonyl clusters.
2.1. Reaction
Reaction of compound 1 and Os3(CO)10(NCMe)2 in refluxing
chlorobenzene solution leads to the hydrido complex -H)
Os3(CO)9(
4-C64H3) (2; 14%), the mononuclear complex
Os(CO)3(
4-C64H4) (3; 37%), and Os3(CO)12 (25%) after purification
(
m
m,h
h
by TLC and crystallization (Scheme 1). It appears that compound 2
is obtained from activation of one ethylene CeH bond of 1 by the
triosmium cluster to generate a m-hydrido, h
4-dienyl bonding motif.
On the contrary, compound 3 is produced by insertion of one
osmium atom into the pentagon facing the ethylene bridge,
together with the Os3 cluster fragmentation. The complex CpCo(h4
-
C64H4) analogous to 3 was previously reported by Rubin and
coworkers [25] from the reaction of CpCo(CO)2 and 1. In contrast,
thermal reaction of Os3(CO)10(NCMe)2 with the pristine fullerene
C60 mainly yielded the face-capping complex Os3(CO)9(m3- , , -
h2 h2 h2
C60) [29].
2.2. Characterization of 2 and 3
Compound 2 forms an air-stable, green solid. The ESI mass
spectrum presents the molecular ion peak at m/z 1600 (192Os),
corresponding to the combination of 1 with an Os3(CO)9 unit. The IR
* Corresponding author. Fax: þ886 7 5253908.
E-mail address: wenyann@mail.nsysu.edu.tw (W.-Y. Yeh).
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.05.034

70
S.-T. Lien, W.-Y. Yeh / Journal of Organometallic Chemistry 715 (2012) 69e72
H
H
H
H
+
Os3(CO)10(NCMe)2
1
reflux
Cl
H
O
H
H
C
H
Os
O
C
( -H)Os3(CO)9( , 4-C64H3)
Os3(CO)12
+
+
C
O
3
2
Fig. 2. 300 MHz 1H NMR spectrum of 2 in the hydrocarbon region taken in CDCl3/CS2
Scheme 1. Preparation of 2 and 3.
at 23 ꢁC, showing the presence of two isomers in a 7:1 ratio.
spectrum in the carbonyl region is shown in Fig. 1, which is similar
to that recorded for the hydrido dienyl complex -H)
Os3(CO)9(
4-C8H11) [30], obtained from thermal reaction of 1,5-
spectrum displays three terminal carbonyl stretchings at 2091,
2029, and 2017 cmꢀ1. The 1H NMR spectrum shows the olefinic
proton resonances at 7.6 ppm, which is downfield shifted by
0.7 ppm compared to 1 (6.9 ppm) (Fig. 3), consistent with
a decrease of electron density on the alkene carbons upon coordi-
nation to the osmium atom.
(
m
m,h
cyclooctadiene and Os3(CO)10(NCMe)2. The 1H NMR spectrum of 2
shows two bridging hydride resonances at ꢀ15.11 and ꢀ15.82 ppm
and two sets of hydrocarbon signals in 6.92e5.81 ppm (Fig. 2),
indicating the presence of two isomers in an approximate 7:1 ratio.
Attempts to separate the two isomers by HPLC or a recrystallization
method were not successful. Presumably, the major isomer 2a
contains a 1,2,6,7-dienyl bonding mode, which persists less steric
interactions between fullerene and Os3 cluster, while the minor
isomer 2b can be assigned to the more congested 1,2,4,5-dienyl
complex.
2.3. Structure description of 3$C7H8
Crystals of 3$C7H8 suitable for an X-ray diffraction study were
grown by slow diffusion of n-hexane into a CS2/toluene solution of
3 at ambient temperature. There are two independent but struc-
turally similar complexes in the asymmetric unit, with the ORTEP
Compound 3 forms an air-stable, red solid. The ESI mass spec-
trum presents the molecular ion peak at m/z 1048 (192Os) with the
isotope distribution matching the Os(CO)3(C64H4) formula. The IR
Fig. 1. Comparison of the IR spectra of (m-H)Os3(CO)9(m,h
4-C8H11) and 2 in the carbonyl
region; obtained in dichloromethane.
Fig. 3. 300 MHz 1H NMR spectrum of 1 and 3 taken in CDCl3/CS2 at 23 ꢁC.

S.-T. Lien, W.-Y. Yeh / Journal of Organometallic Chemistry 715 (2012) 69e72
71
diagram of one shown in Fig. 4. Compound 3 contains an osmium
atom in a distorted octahedral geometry. Remarkably, the C11eC15
edge has been broken by oxidative insertion of the osmium atom
with Os1eC11 2.09(1) Å and Os1eC15 2.11(1) Å, and the non-
bonding C11/C15 distance is 2.54(5) Å. The ethylene moiety is
Os3(CO)10(NCMe)2 [32] and C64H4 (1) [25] were prepared as
described in the literature. Solvents were dried over appropriate
reagents under dinitrogen and distilled immediately before use.
Preparative thin-layer chromatographic (TLC) plates were prepared
from silica gel (Merck). Infrared spectra were recorded on a Jasco
FT/IR-4100 IR spectrometer. 1H and 31P NMR spectra were obtained
on a Bruker Advance 300 spectrometer. Electrospray ionization
(ESI) mass spectra were recorded on a Thermo Finnigan Triple
Quadrupole mass spectrometer.
p
-coordinated to the osmium atom with Os1eC4 2.40(1) Å and
Os1eC5 2.40(1) Å, which are substantially longer than the
OseC2(alkene) distances in Os3(CO)11
2-C60) (av. 2.24 Å) [29],
Os3(CO)10
3-PPh2C60H) (av. 2.23 Å) [31] and Os3(CO)10 4-C8H12
(h
(m,
h
(h
)
(av. 2.31 Å) [30], likely due to steric constraints of the bisfulleroid
ligand. The three terminal carbonyl ligands occupy the facial posi-
tion, with the OseCeO angles ranging from 176(1)e178(1)ꢁ. The
bond lengths Os1eC1 1.98(1) Å and Os1eC2 1.97(1) Å are 0.1 Å
longer than Os1eC3 1.88(1) Å, suggesting a stronger trans-
3.2. Thermal reaction of Os3(CO)10(NCMe)2 and 1
Os3(CO)10(NCMe)2 (29 mg, 0.031 mmol), compound 1 (20 mg,
0.026 mmol) and chlorobenzene (10 ml) were placed in an oven-
dried 50 ml Schlenk flask, equipped with a condenser, under
a dinitrogen atmosphere. The solution was heated to reflux for
15 min. The solvent was then removed under vacuum, and the
residue was subjected to TLC, eluting with CS2. Isolation of the
yellow band afforded Os3(CO)12 (7 mg, 25%), isolation of the green
influence from the Os1eC11 and Os1eC15
the Os1eC4, 5 -bond.
s-bond compared to
p
2.4. Conclusion
band afforded (m-H)Os3(CO)10(m,h
4-C64H3) (2; 4 mg, 14%), and
Reactivity of the bisfulleroid molecule 1 towards triosmium
carbonyl clusters has been investigated. The ethylene bridge of 1
can undergo a CeH bond activation to give 2. On the other hand,
compound 3 is formed by oxidative insertion of one osmium atom
into a five-membered ring of fullerene, leading to an annulene
architecture. However, no endohedral Os-fullerene complexes were
isolated from the reactions. We are currently exploring the reac-
tions of fullerene derivatives with polynuclear clusters, with an aim
to create a large orifice for metal inclusion.
isolation of the red band afforded Os(CO)3(
37%).
h
4-C64H4) (3; 7.1 mg,
3.2.1. Compound 2
Mass (ESI) m/z: 1600 (Mþ, 192Os). IR (CH2Cl2, nCO): 2100s, 2089w,
2076s, 2048w, 2029s, 2017s, 2004w, 1980w, 1967w cmꢀ1. 1H NMR
(CDCl3 þ CS2, 23 ꢁC): 6.92 (d, JHeH ¼ 6 Hz, 1H), 6. 89 (d, JHeH ¼ 6 Hz,
0.15H), 6.81 (d, JHeH ¼ 2 Hz, 0.15H), 6.26 (dd, JHeH ¼ 2 and 6 Hz, 1H),
6.10 (d, JHeH ¼ 2 Hz, 1H), 5.81 (dd, JHeH ¼ 2 and 6 Hz, 0.15H,
3. Experimental
C64H3), ꢀ15.11 (s, 1H), ꢀ15.82 (s, 0.15H,
m-H) ppm. HRMS (ESI) Calc.
for C73H4N3O9Os3: 1599.8854. Found: 1599.8694.
3.1. General methods
3.2.2. Compound 3
Mass (ESI) m/z: 1048 (Mþ, 192Os). IR (CS2, nCO): 2091vs, 2029s,
2017s cmꢀ1. 1H NMR (CDCl3þCS2, 23 ꢁC): 7.63 (m, 2H), 6.66 (m, 2H,
C64H4) ppm. HRMS (ESI) Calc. for C67H4O3Os: 1047.9768. Found:
1047.9772.
All manipulations were carried out under an atmosphere of
purified dinitrogen with standard Schlenk techniques.
3.3. Structure determination of 3$C7H8
The crystal of 3$C7H8 suitable for X-ray analysis was mounted in
a thin-walled glass capillary and aligned on the Nonius Kappa CCD
diffractometer, with graphite-monochromated Mo K
a
radiation
(l
¼ 0.71073 Å). The
q
range for data collection is 1.29e25.03ꢁ. Of
Table 1
Crystallographic data for 3$C7H8.
Formula
T (K)
Crystal system
Space group
Unit cell dimensions
a (Å)
C74H12O3Os
200(2)
Triclinic
P1
Fig. 4. Molecular structure of 3$C7H8 with 30% probability ellipsoids, where the
toluene molecule is artificially omitted. Selected bond distances (Å) and bond angles
(ꢁ): Os1eC1 1.98(1), Os1eC2 1.97(1), Os1eC3 1.88(1), Os1eC4 2.40(1), Os1eC5 2.40(1),
Os1eC11 2.09(1), Os1eC15 2.11(1), C4eC5 1.35(2), C4eC9 1.52(2), C5eC6 1.51(2),
C6eC7 1.53(2), C6eC16 1.52(1), C7eC8 1.36(2), C8eC9 1.54(2), C9eC10 1.50(2),
C10eC111.40(2), C11eC12 1.46(2), C12eC13 1.50(2), C13eC14 1.46(2), C14eC15 1.45(1),
C15eC16 1.38(2) and Os1eC1eO1 176(1), Os1eC2eO2 176(1), Os1eC3eO3 178(1),
Os1eC4eC5 73.8(7), Os1eC4eC9 109.6(7), Os1eC5eC4 73.5(7), Os1eC5eC6 110.1(7),
15.3421(18)
16.5423(18)
17.847(2)
103.299(3)
109.647(2)
104.531(4)
3876.1(8)
4
b (Å)
c (Å)
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
V (Å3)
Z
Dcalc (g cmꢀ3
F(000)
)
1.952
2224
3.360
Os1eC11eC10
120.8(8),
Os1eC11eC12
121.3(8),
Os1eC15eC14
120.5(8),
Os1eC15eC16 120.1(8), C1eOs1eC15 172.1(4), C2eOs1eC11 169.8(4), C3eOs1eC4
162.2(5), C3eOs1eC5 163.7(5), C11eOs1eC15 74.7(4), C4eC5eC6 123(1), C4eC9eC8
112(1), C4eC9eC10 113(1), C5eC6eC7 112.5(9), C5eC6eC16 112(1), C6eC7eC8 123(1),
C6eC16eC15 119(1), C7eC8eC9 122(1), C8eC9eC10 101.7(8), C9eC10eC11 119(1),
C10eC11eC12 116(1), C11eC12eC13 120.4(9), C12eC13eC14 116.8(9), C13eC14eC15
122(1), C14eC15eC16 118(1).
m
(mmꢀ1
)
R1
wR2
0.0626
0.1427
1.086
Goodness-of-fit on F2

72
S.-T. Lien, W.-Y. Yeh / Journal of Organometallic Chemistry 715 (2012) 69e72
[8] A. Ikeda, Y. Kameno, Y. Nakao, H. Sato, S. Sakaki, J. Organomet. Chem. 692
(2007) 299e306.
[9] H.-F. Hsu, J.R. Shapley, J. Organomet. Chem. 599 (2000) 97e105.
[10] M. Halim, R.D. Kennedy, M. Suzuki, S.I. Khan, P.L. Diaconescu, Y. Rubin, J. Am.
Chem. Soc. 133 (2011) 6841e6851.
[11] T. Akasaka, S. Nagase, Endofullerenes, Kluwer Academic Publishers, Dor-
drecht, Netherlands, 2002.
[12] H. Shinohara, Rep. Prog. Phys. 63 (2000) 843e892.
[13] R.E. Smalley, Acc. Chem. Res. 25 (1992) 98e105.
the 28,175 reflections collected, 13,581 reflections were indepen-
dent. All data were corrected for Lorentz and polarization effects
and for the effects of absorption. The structure was solved by the
direct method and refined by least-square 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.
[14] M.N. Chaur, F. Melin, A.L. Ortiz, L. Echegoyen, Angew. Chem. Int. Ed. 48 (2009)
7514e7538.
[15] J.R. Heath, S.C. O’Brien, Q. Zhang, Y. Liu, R.F. Curl, F.K. Tittel, R.E. Smalley, J. Am.
Chem. Soc. 107 (1985) 7779e7780.
[16] M. Takata, B. Umeda, E. Nishibori, M. Sakata, Y. Saito, M. Ohno, H. Shinohara,
Nature 337 (1995) 46e49.
[17] H. Umemoto, K. Ohashi, T. Inoue, N. Fukui, T. Sugai, H. Shinohara, Chem.
Commun. 46 (2010) 5653e5655.
[18] H. Yang, C. Lu, Z. Liu, H. Jin, Y. Che, M.M. Olmstead, A.L. Balch, J. Am. Chem. Soc.
130 (2008) 17296e17300.
Acknowledgements
This work was financially supported by the National Science
Council of Taiwan. We thank Mr. Ting-Shen Kuo (National Taiwan
Normal University, Taipei) for X-ray diffraction analysis.
[19] T. Wakahara, H. Nikawa, T. Kikuchi, T. Nakahodo, G.M. Aminur Rahman,
T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, E. Horn, K. Yamamoto, N. Mizorogi,
Z. Slanina, S. Nagase, J. Am. Chem. Soc. 128 (2006) 14228e14229.
[20] B.Q. Mercado, M.A. Stuart, M.A. Mackey, J.E. Pickens, B.S. Confait, S. Stevenson,
M.L. Easterling, R. Valencia, A. Rodríguez-Fortea, J.M. Poblet, M.M. Olmstead,
A.L. Balch, J. Am. Chem. Soc. 132 (2010) 12098e12105.
[21] K. Komatsu, M. Murata, Y. Murata, Science 307 (2005) 238e240.
[22] M. Murata, Y. Murata, K. Komatsu, Chem. Commun. (2008) 6083e6094.
[23] Y. Rubin, Top. Curr. Chem. 199 (1999) 67e91.
Appendix A. Supplementary material
CCDC 867710 for 3 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Center via www.ccdc.cam.ac.
uk/data_request/cif.
[24] B. Nuber, A. Hirsch, Chem. Commun. (1996) 1421e1422.
[25] M.-J. Arce, A.L. Viado, Y.-Z. An, S.I. Khan, Y. Rubin, J. Am. Chem. Soc. 118 (1996)
3775e3776.
References
[26] W.-Y. Yeh, Chem. Commun. 47 (2011) 1506e1508.
[27] Y.-Y. Wu, W.-Y. Yeh, Organometallics 30 (2011) 4792e4795.
[28] W.-Y. Yeh, Angew. Chem. Int. Ed. 50 (2011) 12046e12049.
[29] J.T. Park, H. Song, J.-J. Cho, M.-K. Chung, J.-H. Lee, I.-H. Suh, Organometallics 17
(1998) 227e236.
[1] A. Hirsch, M. Brettreich, Fullerenes, Wiley-VCH, Weinheim, Germany, 2005.
[2] A. Krueger, Carbon Materials and Nanotechnology, Wiley-VCH, Weinheim,
Germany, 2010.
[3] A.L. Balch, M.M. Olmstead, Chem. Rev. 98 (1998) 2123e2166.
[4] Y. Matsuo, E. Nakamura, Chem. Rev. 108 (2008) 3016e3028.
[5] K. Lee, H. Song, J.T. Park, Acc. Chem. Res. 36 (2003) 78e86.
[6] C.-H. Chen, C.-S. Chen, H.-F. Dai, W.-Y. Yeh, Dalton Trans. 41 (2012)
3030e3037.
[30] Y.-C. Liu, W.-Y. Yeh, G.-H. Lee, S.-M. Peng, J. Organomet. Chem. 689 (2004)
1944e1948.
[31] W.-Y. Yeh, K.-Y. Tasi, Organometallics 29 (2010) 604e609.
[32] D. Braga, F. Grepioni, E. Parisini, B.F.G. Johnson, C.M. Martin, J.G.M. Nairn,
J. Lewis, M. Martinelli, J. Chem. Soc. Dalton Trans. (1993) 1891e1895.
[7] H.-F. Hsu, J.R. Shapley, J. Am. Chem. Soc. 118 (1996) 9192e9193.