Synthesis and crystal structures of two isomerically pure organotransition-metal [60]fullerene derivatives containing dppb ligands: mer-M(CO)3(dppb)(η2-C60) (M = Mo, W)

Article abstract of DOI:10.1021/om990975w

The reaction of M(CO)₃(CH₃CN)₃ (M = Mo, W) with an equimolar quantity of 1,2-bis-(diphenylphosphino)benzene (dppb) results in formation of fac-M(CO)₃(dppb) (CH₃CN) (1, M = Mo, 73%; 2, M = W, 62%). Int

Full text of DOI:10.1021/om990975w

Organometallics 2000, 19, 1643-1647
1643
Syn th esis a n d Cr ysta l Str u ctu r es of Tw o Isom er ica lly
P u r e Or ga n otr a n sition -Meta l [60]F u ller en e Der iva tives
Con ta in in g d p p b Liga n d s: m er -M(CO)3(d p p b)(η2-C60) (M
) Mo, W)
Li-Cheng Song,* J in-Ting Liu, Qing-Mei Hu, and Lin-Hong Weng
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry,
Nankai University, Tianjin 300071, China
Received December 8, 1999
The reaction of M(CO)3(CH3CN)3 (M ) Mo, W) with an equimolar quantity of 1,2-bis-
(diphenylphosphino)benzene (dppb) results in formation of fac-M(CO)3(dppb) (CH3CN) (1,
M ) Mo, 73%; 2, M ) W, 62%). Interaction of 1 or 2 with [60]fullerene in chlorobenzene at
about 80 °C gives the isomerically pure isomers mer-M(CO)3(dppb)(η2-C60) (3, M ) Mo, 76%;
4, M ) W, 66%). All the new compounds 1-4 have been characterized by elemental analysis
and spectroscopic methods, as well as by single-crystal X-ray diffraction analysis for 3 and
4.
In tr od u ction
(dppb)(CH3CN) can be easily replaced by [60]fullerene
to give isomerically pure fac-M(CO)3(dppe)(η2-C60) (M
) Cr, Mo)7a,b and an isomeric mixture of fac-/ mer-
W(CO)3(dppb)(η2-C60),7c respectively. Herein we further
report the extended studies about this type of substitu-
tion reaction of C60 with fac-M(CO)3(dppb)(CH3CN) (M
) Mo, W) to give the pure isomer mer-M(CO)3(dppb)-
(η2-C60) (M ) Mo, W) and the first X-ray crystal
structures of metal fullerene derivatives containing
dppb ligands.
Since the discovery of [60]fullerene1 and its synthesis
in large-scale amounts,2 the organometallic chemistry
of C60, primarily including the synthesis, structural
characterization, and properties of transition-metal [60]-
fullerene complexes, has attracted great attention.3
From the viewpoint of coordination chemistry, C60 might
be ligated to metals in all conceivable ways from η1 to
η6, and actually a variety of such transition-metal
fullerene derivatives have already been prepared and
characterized.3,4 Vaska-type complexes react with C60
to give its C60 adducts.5 Photolysis of M(CO)4(dppe) (M
) Mo, W) and C60 produces the CO substitution products
M(CO)3(dppe)(η2-C60).6 In our preliminary reports,7 we
have indicated that the acetonitrile ligand in fac-
M(CO)3(dppe)(CH3CN) (M ) Cr, Mo) or fac-W(CO)3
Resu lts a n d Discu ssion
Syn th esis a n d Ch a r a cter iza tion of fa c-M(CO)3-
(d p p b)(CH3CN) (1, M ) Mo; 2, M ) W). Reaction of
M(CO)3(CH3CN)3 with an equimolar quantity of 1,2-bis-
(diphenylphosphino)benzene (dppb) in boiling acetoni-
trile resulted in formation of 1 and 2 in 73% and 62%
yields, as shown in eq 1.
* To whom correspondence should be addressed. Fax: 0086-22-
23504853. E-mail: lcsong@public.tpt.tj.cn.
(1) Kroto, H. W.; Heath, J . R.; O’Brien, S. C.; Curl, R. F.; Smalley,
R. E. Nature 1985, 318, 162.
(2) Kra¨schmer, W.; Lamb, L. D.; Fostiropoulos, K.; Huffman, D. R.
Nature 1990, 347, 354.
CH3CN
M(CO)3(CH3CN)3 + dppb
8
reflux
(3) For reviews, see: (a) Balch, A. L.; Olmstead, M. M. Chem. Rev.
1998, 98, 2123. (b) Fagan, P. J .; Calabrese, J . C.; Malone, B. Acc. Chem.
Res. 1992, 25, 134. (c) Sliwa, W. Transition Met. Chem. 1996, 21, 583.
(4) (a) Sokolov, V. I. Dokl. Akad. Nauk SSSR 1992, 326, 647. (b)
Zhang, S.; Brown, T. L.; Du, Y.; Shapley, J . R. J . Am. Chem. Soc. 1993,
115, 6705. (c) Ballenweg, S.; Gleiter, R.; Kra¨tschmer, W. Tetrahedron
Lett. 1993, 34, 3737. (d) Ballenweg, S.; Gleiter, R.; Kra¨tschmer, W. J .
Chem. Soc., Chem. Commun. 1994, 2269. (e) Fagan, P. J .; Calabrese,
J . C.; Malnone, B. Science 1991, 252, 1160. (f) Bashilov, V. V.;
Petrovskii, P. V.; Sokolov, V. I.; Lindeman, S. V.; Guzey, I. A.;
Struchkov, Y. T. Organometallics 1993, 12, 991. (g) Park, J . T.; Song,
H.; Cho, J .-J .; Chung, M.-K.; Lee, J .-H.; Suh, I.-H. Organometallics
1998, 17, 227. (h) Chernega, A. N.; Green, L. H.; Haggitt, J .; Stephens,
A. H. H. J . Chem. Soc., Dalton Trans. 1998, 755. (i) Tang, K.; Zheng,
S.; J in, X.; Gu, Z.; Zhou, X.; Tang, Y. J . Chem. Soc., Dalton Trans.
1997, 3585. (j) Wijnkoop, M. V.; Meidine, M. F.; Avent, A. G.; Darwish,
A. D.; Kroto, H. W.; Taylor, R.; Walton, R. M. J . Chem. Soc., Dalton
Trans. 1997, 675. (k) Rasinkangas, M.; Pakkaned, T. T.; Pakkaned,
T. A.; Ahlgren, M.; Rouvinen, J . J . Am. Chem. Soc. 1993, 115, 4901.
(l) Mavunkal, I. J .; Chi, Y.; Peng, S.-M.; Lee, G.-H. Organometallics
1995, 14, 4454. (m) Sawamura, M.; Iikkura, H.; Nakamura, E. J . Am.
Chem. Soc. 1996, 118, 12850. (n) Lee, K.; Shapley, J . R. Organome-
tallics 1998, 17, 3020. (o) Song, H.; Lee, K.; Park, J . T.; Choi, M.-G.
Organometallics 1998, 17, 4477.
fac-M(CO)3(dppb)(CH3CN) (1)
1, M ) Mo; 2, M ) W
Compounds 1 and 2 are yellow crystals, both air-
sensitive, especially in solution. In theory 1 or 2 might
exist as another isomeric form, namely the mer isomer
(Chart 1). However, spectroscopic studies have shown
that 1 and 2 are actually fac isomers (Chart 1).
(5) (a) Balch, A. L.; Catalano, V. J .; Lee, J . W.; Olmstead, M. M. J .
Am. Chem. Soc. 1992, 114, 5455. (b) Balch, A. L.; Lee, J . W.; Noll, B.
C.; Olmstead, M. M. J . Am. Chem. Soc. 1992, 114, 10984. (c) Balch, A.
L.; Lee, J . W.; Noll, B. C.; Olmstead, M. M. Inorg. Chem. 1994, 33,
5238. (d) Balch, A. L.; Catalano, V. J .; Lee, J . W. Inorg. Chem. 1991,
30, 3980.
(6) Hsu, H.-F.; Du, Y.; Albrecht-Schmitt, T. E.; Wilson, S. R.;
Shapley, J . R. Organometallics 1998, 17, 1756.
(7) (a) Song, L.-C.; Zhu, Y.-H.; Hu, Q.-M. J . Chem. Res., Synop. 1999,
56. (b) Song, L.-C.; Zhu, Y.-H.; Hu, Q.-M. Polyhedron 1998, 17, 469.
(c) Song, L.-C.; Zhu, Y.-H.; Hu, Q.-M. Polyhedron 1997, 16, 2141.
10.1021/om990975w CCC: $19.00 © 2000 American Chemical Society
Publication on Web 03/31/2000

1644 Organometallics, Vol. 19, No. 9, 2000
Song et al.
Ch a r t 1
Ch a r t 2
For example, the 31P NMR spectra display only one
singlet at 60.74 ppm for 1 and 54.00 ppm for 2, which
is consistent with the fac isomers having two P atoms
in the same chemical environment. The mer isomer
should be expected to display two 31P NMR resonances,
since they have two magnetically different P atoms.8 In
each of the 1H NMR spectra of 1 and 2 there is a
multiplet around 7.40 ppm, assigned to the phenyl and
phenylene groups of the dppb ligand, and a singlet at
1.99 ppm for 1 and 1.86 ppm for 2, assigned to the
methyl group of the CH3CN ligand. The IR spectra of 1
and 2 are also consistent with their fac structures,
which are expected to show three absorption bands
but the two P atoms are different in the mer isomer.
The 31P NMR spectrum of 3 shows two doublets at 66.18
and 55.66 ppm (J P-P ) 15.4 Hz), and that of 4 exhibits
two apparent singlets (the J P-P values are too small to
be recognized as two doublets) at 43.49 and 49.50 ppm.
This indicates two different P atoms are present in 3
and 4; thus, they should be the pure mer isomers. The
IR spectra of 3 and 4 display four bands in the range
1432-524 cm-1 for their C60 cores and three bands in
the region 2007-1884 cm-1 for their terminal carbonyls.
This is also in good agreement with the fact that 3 and
4 are single isomers, since the isomer mixture would
have more IR-active bands for their CO ligands.10
In the UV-vis spectra of 3 and 4, the intense bands
between 200 and 400 nm are close to those of free C60.
This is typical of a [60]fullerene cage which has been
modified slightly by complexation.11 The biggest changes
in the spectra, compared to that of free C60, appear in
the visible range. A new band at 437.5 nm appears for
3 and at 433.5 nm for 4, which is the reason for the
color change of the reaction mixture from purple C60 to
the dark green 3 and 4. The presence of a weak and
broad band at 430-440 nm suggests a useful diagnostic
rule for η2-C60 compounds.4h,12
around the region 1800-1930 cm-1 9
.
Syn th esis a n d Ch a r a cter iza tion of m er -M(CO)3-
(d p p b)(η2-C60) (3, M ) Mo; 4, M ) W). When an
equimolar quantity of 1 or 2 was added to a solution of
[60]fullerene in chlorobenzene, followed by heating the
mixture at about 80 °C for 6 h, a dark green solution
was formed. Further separation and purification by
column chromatography afforded isomerically pure 3 in
67% yield and 4 in 66% yield, as shown in eq 2.
+ C60 chlorobenzene8
fac-M(CO) (dppb)(CH CN)
3
1, M ) Mo; 2, M ) 3W
80 °C
mer-M(CO)3(dppb)(η2C60) (2)
3, M ) Mo; 4, M ) W
A series of 13C NMR studies of the C60 moiety for
numerous metallofullerenes have been reported: e.g.,
for Rh(NO)(PPh3)2(η2-C60) (Cs symmetry, showing 31 sp2
and 1 sp3 resonance signal),13 Fe(CO)4(η2-C60) (C2v,
showing 16 sp2 and 1 sp3 resonance signal),14 and Os3-
(CO)9(PMe3)(η2-C60) (C2v, showing 16 sp2 and 1 sp3
resonance signal).4g The chemical shifts of sp2 and sp3
carbon atoms of the C60 core are typically in the regions
of 175-135 and 85-50 ppm, respectively. Although 3
has Cs symmetry, there are only 20 signals in the region
165-135 ppm in its 13C NMR spectrum for the carbon
atoms of its C60 core. Among the 20 signals, 10 could be
assigned to four carbon atoms each and the other 10
might be assigned to two carbon atoms each. This
implies that the C60-metal moiety rotation is present
in the solution at room temperature, which causes the
number of 13C NMR signals of C60 moiety to vary from
a 32-line pattern of Cs symmetry to a 17-line pattern of
C2v symmetry and finally to give the number of 13C
NMR signals in between.13
The formation of only mer isomers implies that the
displacement of CH3CN by C60 occurred with the
complete conversion of the fac configuration of the
starting materials under these conditions. However, as
previously indicated for the reaction of 2 with C60 under
other conditions, for example, if an equimolar amount
of [60]fullerene was added to a chlorobenzene solution
of 2 followed by heating this mixture at about 80 °C,
all that was obtained was an isomeric mixture of fac-
and mer-W(CO)3(dppb)(η2-C60).7c The structural formu-
las of these fac and mer isomers are shown in Chart 2.
Compounds 3 and 4 are stable to air and heat and
are soluble in polar solvents such as chloroform, toluene,
THF, carbon disulfide, and chlorobenzene to form green
solutions but are not soluble in nonpolar solvents such
as petroleum ether. 3 and 4 have been fully character-
ized by elemental analysis and spectroscopy. Formula-
tion of 3 was established by its FAB mass spectrum with
a molecular ion (M+) peak at m/z 1438. As was the case
for their precursors 1 and 2, the products 3 and 4 might
exist as fac isomers, as mer isomers, or as a mixture of
the two. As mentioned above, the fac isomer has two
identical P atoms in the same chemical environment,
(10) Collman, J . P.; Hegedus, L. S. Principles and Applications of
Organotransition Metal Chemistry; University Science Books: Mill
Valley, CA, 1980; p 85.
(11) (a) Hare, J . P.; Kroto, H. W.; Taylor, R. Chem. Phys. Lett. 1991,
177, 394. (b) Akasaka, T.; Ando, W.; Kobagashi, K.; Nagase, S. J . Am.
Chem. Soc. 1993, 115, 1605.
(12) Hirsch, A.; Gro¨sser, T.; Skiebe, A.; Soi, A. Chem. Ber. 1993,
126, 1061.
(8) (a) Issacs, E. E.; Graham, W. A. G. Inorg. Chem. 1975, 14, 2560.
(b) Bond, A. M.; Colton, R.; McGregor, K. Inorg. Chem. 1986, 25, 2378.
(9) Darenburg, D. J .; Zalewski, D. J .; Plepys, C.; Campana, C. Inorg.
Chem. 1987, 26, 3727.
(13) Green, M. L. H.; Stephens, A. H. H. J . Chem. Soc., Chem.
Commun. 1997, 793.
(14) Douthwaite, R. E.; Green, M. L. H.; Stephens, A. H. H.; Turner,
J . F. C. J . Chem. Soc., Chem. Commun. 1993, 1522.

Organotransition-Metal [60]Fullerene Derivatives
Organometallics, Vol. 19, No. 9, 2000 1645
F igu r e 1. ORTEP diagram of 3 with ellipsoids drawn at 30% probability.
F igu r e 2. ORTEP diagram of 4 with ellipsoids drawn at 30% probability.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 3
Mo(1)-C(103)
Mo(1)-C(102)
Mo(1)-C(1)
Mo(1)-P(2)
C(1)-C(6)
2.002(5)
2.042(4)
2.325(3)
2.5479(10)
1.482(5)
1.486(5)
Mo(1)-C(101)
Mo(1)-C(2)
Mo(1)-P(1)
C(1)-C(2)
2.019(4)
2.313(3)
2.4908(10)
1.477(5)
1.486(5)
1.489(5)
C(1)-C(9)
C(2)-C(3)
C(2)-C(12)
C(103)-Mo(1)-C(101)
C(101)-Mo(1)-C(102)
C(101)-Mo(1)-C(2)
C(103)-Mo(1)-C(1)
C(102)-Mo(1)-C(1)
C(103)-Mo(1)-P(1)
C(102)-Mo(1)-P(1)
C(1)-Mo(1)-P(1)
93.23(17)
179.63(14)
89.06(14)
74.84(14)
91.53(13)
84.72(12)
93.70(10)
158.57(9)
90.04(12)
86.84(9)
C(103)-Mo(1)-C(102)
C(103)-Mo(1)-C(2)
C(102)-Mo(1)-C(2)
C(101)-Mo(1)-C(1)
C(2)-Mo(1)-C(1)
86.67(16)
111.84(14)
90.65(13)
88.10(14)
37.12(12)
86.65(11)
163.12(9)
161.07(12)
90.17(10)
123.94(9)
C(101)-Mo(1)-P(1)
C(2)-Mo(1)-P(1)
C(103)-Mo(1)-P(2)
C(102)-Mo(1)-P(2)
C(1)-Mo(1)-P(2)
C(101)-Mo(1)-P(2)
C(2)-Mo(1)-P(2)
P(1)-Mo(1)-P(2)
76.85(3)
Cr ysta l Molecu la r Str u ctu r es of 3 a n d 4. The
molecular structures of 3 and 4 were unambiguously
confirmed by a single-crystal X-ray study. The molecular
structural diagrams of 3 and 4 are shown in Figures 1
and 2, respectively, whereas Tables 1 and 2 list the
selected bond lengths and angles.
For each of the two compounds, the C60 ligand is
bound in a η2 fashion to the metal center M(1) (M )
Mo, W), with the C(1)-C(2) bond between two six-
membered rings. The metal center has a slightly
distorted octahedral geometry. The atoms M(1), C(1),
C(2), C(103), P(1), and P(2) are coplanar (the plane

1646 Organometallics, Vol. 19, No. 9, 2000
Song et al.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 4
and W(CO)3(CH3CN)3 were prepared according to literature
procedures.15 Products were separated by thin-layer chroma-
tography (TLC glass plates of 20 × 25 × 0.25 cm coated with
silica gel 60H) or by column chromatography (30 × 2.5 cm
column with silica gel). Melting points were determined on a
Yanaco MP-500 melting point apparatus. Elemental analysis
and FAB-MS were performed on a Yanaco CHN Corder MT-3
analyzer and a Zabspec spectrometer, respectively. IR and
UV-vis spectra were recorded on a Bio-Rad FTS 135 and a
W(1)-C(101)
W(1)-C(102)
W(1)-C(1)
W(1)-P(2)
C(1)-C(6)
1.990(10)
2.007(9)
2.295(7)
2.526(2)
1.494(11)
1.470(11)
W(1)-C(103)
W(1)-C(2)
W(1)-P(1)
C(1)-C(9)
C(1)-C(2)
C(2)-C(3)
2.003(11)
2.291(8)
2.483(2)
1.470(11)
1.501(11)
1.487(11)
C(2)-C(12)
C(101)-W(1)-C(103)
C(103)-W(1)-C(102)
C(103)-W(1)-C(2)
C(101)-W(1)-C(1)
C(102)-W(1)-C(1)
C(101)-W(1)-P(1)
C(102)-W(1)-P(1)
C(1)-W(1)-P(1)
93.9(4)
86.3(4)
112.6(3)
89.0(3)
90.9(3)
86.7(3)
93.6(2)
158.0(2)
160.7(3)
86.4(2)
77.04(8)
C(101)-W(1)-C(102) 179.7(4)
1
C(101)-W(1)-C(2)
C(102)-W(1)-C(2)
C(103)-W(1)-C(1)
C(2)-W(1)-C(1)
C(103)-W(1)-P(1)
C(2)-W(1)-P(1)
89.2(3)
90.5(3)
74.5(3)
38.2(3)
84.2(3)
162.91(19)
89.6(3)
90.3(2)
124.6(2)
Shimadzu UV-2401/PC spectrometer, respectively. H NMR,
31P NMR, and 13C NMR spectra were obtained on Bruker AC-
P200 and UNITY-PLUS 400 spectrometers.
Syn th esis of fa c-Mo(CO)3(d p p b)(CH3CN) (1). A 100 mL
three-necked flask equipped with a stir bar, a rubber septum,
and a reflux condenser topped with a nitrogen inlet tube was
charged with 0.151 g (0.50 mmol) of Mo(CO)3(CH3CN)3, 0.223
g (0.50 mmol) of dppb, and 40 mL of acetonitrile. The mixture
was stirred and heated to reflux for 24 h. The warm solution
was filtered and refrigerated overnight. A crop of bright yellow
crystals of fac-Mo(CO)3(dppb)(CH3CN) (1) was isolated (0.243
C(101)-W(1)-P(2)
C(102)-W(1)-P(2)
C(1)-W(1)-P(2)
C(103)-W(1)-P(2)
C(2)-W(1)-P(2)
P(1)-W(1)-P(2)
equation gives a mean deviation of 0.0668 Å for 3). A
mer configuration is adopted for the dppb and [60]-
fullerene ligands, where one phosphorus atom, P(1), of
the chelating diphosphine ligand is trans to the olefin
center and the other, P(2), is cis to that center. Because
of the trans effect of carbonyl ligand C(103)O(3) is
stronger than that of C60 ligand, the M(1)-P(2) bond
length is longer than that of M(1)-P(1) (2.5479(10) and
2.4908(10) Å for 3 and 2.526(2) and 2.483(2) Å for 4,
respectively). The bite angles of the dppb ligand, P(1)-
M(1)-P(2), are almost identical in 3 and 4 (76.85° for 3
and 77.04° for 4), but they are slightly smaller than that
of the dppe ligand in Mo(CO)3(dppe)(η2-C60) (77.5°).6
The two coordinated carbon atoms, C(1) and C(2), are
pulled away from the fullerene cage; coincident with this
is a lengthening of the four bonds adjacent to C(1) and
C(2) (average 1.486 Å for 3 and 1.480 Å for 4). The C(1)-
C(2) bond lengths are 1.477(5) Å for 3 and 1.501(11) Å
for 4, which are significantly longer than that in free
C60 (6,6-ring junction bond length 1.38 Å) and the
average length (1.390 Å for 3 and 1.384 Å for 4) of the
other 29 6,6-bonds in 3 and 4, due to the metal-to-C60
π-back-donation.3b Such bond lengthening is also ob-
served in other η2-C60 metal complexes, such as in Pt-
(PPh3)2(η2-C60) (1.50(3) Å),4e Pd(PPh3)2(η2-C60) (1.45(3)
Å),4f W(CO)3(dppe)(η2-C60) (1.50(1) Å),6 Mo(CO)3(dppe)-
(η2-C60) (1.483(10) Å),6 Os3(CO)11(η2-C60) (1.42(3) Å),4g
RuCl(NO)(PPh3)2(η2-C60) (1.489 Å),4h and Ir(CO)Cl-
(PPh3)2(η2-C60) (1.53(3) Å).5d The C(1)-C(2) bond of 4 is
longer than that of 3, implying that the π-back-donation
in 4 is stronger than that of 3.
g, 73%). Mp: 223-225 °C dec. Anal. Calcd for
C35H27-
MoNO3P2: C, 62.98; H, 4.08; N, 2.10. Found: C, 63.00; H, 4.33;
N, 2.10. IR (KBr): νCtO 1929 (vs), 1858 (vs), 1811 (vs) cm-1
.
UV-vis (THF, 3.25 × 10-5 M): λmax (log ꢀ) 238.6 nm (4.410).
1H NMR (CDCl3, TMS): 1.99 (s, 3H, CH3), 7.20-7.52 (m, 24H,
4C6H5, C6H4) ppm. 31P NMR (81 MHz, CDCl3, H3PO4): 60.74
(s) ppm.
Syn th esis of fa c-W(CO)3(d p p b)(CH3CN) (2). The same
procedure as for 1 was followed, but 0.196 g (0.50 mmol) of
W(CO)3(CH3CN)3 was used instead of Mo(CO)3(CH3CN)3. A
total of 0.235 g (62%) of 2 was obtained as yellow crystals.
Mp: 210-212 °C dec. Anal. Calcd for C35H27NO3P2W: C, 55.65;
H, 3.60; N, 1.85. Found: C, 55.35; H, 4.04; N, 1.80. IR (KBr):
νCtO 1922 (vs), 1850 (vs), 1805 (vs) cm-1. UV-vis (chloroben-
zene, 2.00 × 10-4 M): λmax (log ꢀ) 288.5 nm (3.982). H NMR
1
(CDCl3, TMS): 1.86 (s, 3H, CH3), 6.88-7.82 (m, 24H, 4C6H5,
C6H4) ppm. 31P NMR (81 MHz, CDCl3, H3PO4): 54.00 (s) ppm.
Syn th esis of m er -Mo(CO)3(d p p b)(η2-C60) (3). A 100 mL
three-necked flask equipped with a stir bar, a N2 inlet tube,
and a serum cap was charged with 0.050 g (0.069 mmol) of
C60 and 75 mL of chlorobenzene. The mixture was stirred at
room temperature until all C60 was dissolved. To the solution
was added 0.047 g (0.069 mmol) of complex 1, and the reaction
mixture was heated to about 80 °C and stirred at this
temperature for 6 h, during which time the purple solution
turned dark green. The resulting solution was evaporated
under vacuum, and the residue was separated by column
chromatography using 1/2 (v/v) toluene/light petroleum ether
as eluent under anaerobic conditions. From the first purple
band was obtained 0.010 g of unchanged C60, and from the
chlorophyll green band was obtained 0.057 g (76% based on
consumed C60) of 3 as a dark green solid. Recrystallization from
THF and pentane gave the complex 3‚3THF as dark green
Finally, it should be noted that fullerene-arene
interactions are observed in 3 and 4. The distances from
the phenyl ring plane center of C(151) through C(156)
to the closest carbon atom C(12) of the C60 moiety of 3
and to the closest C(14) of 4 are 3.1531 and 3.221 Å,
respectively. These distances are very close to that (3.10
Å) in the crystal structure of Ir(CO)Cl(bobPPh2)2(η2-C60),
which also has such intramolecular π-π interactions.5a
crystals. Mp: 237-240 °C dec. Anal. Calcd for
C105H48-
MoO6P2: C, 80.67; H, 3.09. Found: C, 81.07; H, 2.65%. IR
(KBr): νCtO 2007 (s), 1945 (s), 1892 (vs) cm-1; νC 1431 (m),
60
1185 (w), 595 (m), 524 (s) cm-1. UV-vis (THF, 5.80 × 10-6
M): λmax (log ꢀ) 238.5 (5.077), 257.0 (5.204), 343.5 (4.643), 437.5
1
(4.255), 638.5 (3.992) nm. H NMR (CDCl3, TMS): 1.85 (t, 12
H, CH2, J ) 5.0 Hz), 3.72 (t, 12 H, CH2O, J ) 5.0 Hz), 7.24-
7.44 (m, 24 H, 4C6H5, C6H4) ppm. 31P NMR (CDCl3, H3PO4):
66.18 (d, 1P, J P-P ) 15.4 Hz), 55.66 (d, 1P, J P-P ) 15.4 Hz)
ppm. FAB-MS: m/z 720 (C60+), 1348 [Mo(CO)3(dppb)(η2-C60)+,
98Mo]. 13C NMR (100.6 MHz, C4D8O, TMS, 25 °C): 217.97 (1C,
CO), 210.81 (1C, CO), 209.89 (1C, CO), 164.96 (4C), 148.09
(4C), 146.99 (2C), 146.28 (4C), 145.92 (2C), 145.80 (4C), 145.40
(4C), 145.36 (4C), 145.03 (2C), 144.86 (2C), 144.67 (2C), 144.55
(4C), 144.37 (4C), 143.46 (4C), 143.24 (4C), 142.84 (2C), 141.49
Exp er im en ta l Section
Gen er a l Com m en ts. All reactions were carried out under
an atmosphere of highly prepurified nitrogen using standard
Schlenk or vacuum-line techniques. Acetonitrile and chlo-
robenzene were dried by distillation from P2O5 and CaH2 under
nitrogen. Pentane and THF were distilled under nitrogen from
sodium/benzophenone ketyl. [60]Fullerene (99.9%) and dppb
were of commercial origin. The complexes Mo(CO)3(CH3CN)3
(15) Tate, D. P.; Knipple, W. R.; Augl, J . M. Inorg. Chem. 1962, 1,
433.

Organotransition-Metal [60]Fullerene Derivatives
Organometallics, Vol. 19, No. 9, 2000 1647
Ta ble 3. Cr ysta l Da ta a n d Str u ctu r e Refin em en ts
for 3 a n d 4
a dark green solid. Recrystallization from THF and pentane
afforded the complex 4‚3THF as dark green crystals. Mp:
235-238 °C dec. Anal. Calcd for C105H48O6P2W: C, 76.37; H,
2.93. Found: C, 76.51; H, 2.94. IR (KBr): νCtO 2006 (s), 1942
3‚3THF
4‚3THF
mol formula
mol wt
temp/K
cryst syst
space group
a/Å
C
105H48MoO6P2
C105H48O6P2W
1651.22
293
P1h
triclinic
15.0228(17)
16.0718(19)
16.4052(19)
115.885(2)
98.638(3)
100.209(3)
3389.3(7)
2
(s), 1885 (vs); νC 1432 (m), 1185 (w), 583 (w), 524 (s) cm-1
.
60
1563.31
298
P1h
UV-vis (THF, 7.28 × 10-6 M): λmax (log ꢀ): 238.0 (4.997), 257.0
(5.098), 342.5 (4.576), 433.5 (4.143), 613.5 (3.695) nm. 1H NMR
(CS2, TMS): 1.79 (br, 12 H, CH2), 3.59 (br, 12 H, CH2O), 7.24-
7.59 (m, 24H, 4C6H5, C6H4) ppm. 31P NMR (81 MHz, CS2, H3-
PO4): 43.49 (s, 1P), 49.50 (s, 1P) ppm.
triclinic
15.1176(19)
16.2145(19)
16.543(2)
116.141(2)
98.869(2)
99.836(3)
3463.9(7)
2
b/Å
c/Å
X-r a y Cr ysta llogr a p h y. Single crystals of 3 and 4 suitable
for X-ray diffraction analyses were grown by slow diffusion of
n-pentane into their THF solutions at about 5 °C under
nitrogen. The single crystal of 3 (0.035 × 0.084 × 0.22 mm)
and that of 4 (0.30 × 0.25 × 0.20 mm) were glued to a glass
fiber and mounted on a Bruker SMART 1000 automated
diffractometer. Data were collected at room temperature, using
Mo KR graphite-monochromated radiation (λ ) 0.710 73 Å)
in the ω scanning mode. Absorption corrections were per-
formed using SADABS for both 3 and 4. The structures were
solved by direct methods using the SHELXTL-97 program and
refined by full-matrix least-squares techniques (SHELXL-97)
on F2. Hydrogen atoms were located by using the geometric
method. The weighting scheme w ) 1/σ2(Fo2) + (0.0911P)2
R/deg
â/deg
γ/deg
V/Å3
Z
Dc/(g cm-3
)
1.499
1.618
scan type
ω scans
0.303
ω scans
1.821
abs coeff (mm-1
)
F(000)
1596
1660
θ range for data collecn/deg
no. of rflns
1.42-25.03
14 484
1.43-25.03
17 765
no. of indep rflns
12 171
11 894
(Rint ) 0.0391)
(Rint ) 0.0734)
completeness to θ ) 25.03°/% 99.4
99.3
no. of data/restraints/params 12 171/16/1028
11 894/27/942
0.999
2
(where P ) (Fo + 2Fc2)/3) was applied to the data for 3, and
goodness of fit on F2
1.010
w ) 1/σ2(Fo2) + (0.060P)2 (where P ) (Fo2 + 2Fc )/3) was applied
2
final R indices (I > 2σ(I))
R1 ) 0.0511,
wR2 ) 0.1320
R1 ) 0.0784,
wR2 ) 0.1475
0.537 and
R1 ) 0.0679,
wR2 ) 0.1309
R1 ) 0.1233,
wR2 ) 0.1487
1.193 and
-1.368
to the data for 4. The crystal data and structural refinement
details are listed in Table 3.
R indices (all data)
largest diff peak and
hole/(e Å-3
)
-0.373
Ack n ow led gm en t. We are grateful to the National
Natural Science Foundation of China, the Research
Fund for the Doctoral Program of Higher Education of
China, and the Laboratory of Organometallic Chemistry
for financial support.
(2C), 138.07 (2C), 137.71 (2C), 135.24 (2C) (C60 resonances),
134.88 (2C), 134.24 (2C), 133.79 (2C), 133.35 (8C), 131.47 (2C),
130.69 (4C), 129.71 (2C), 129.47 (8C) (dppb resonances) ppm.
Syn t h esis of m er -W(CO)3(d p p b )(η2-C60) (4). The same
procedure as for 3 was followed, but 0.036 g (0.05 mmol) of
Su p p or tin g In for m a tion Ava ila ble: Full tables of crystal
data, atomic coordinates and thermal parameters, and bond
lengths and angles for 3 and 4. This material is available free
of charge via the Internet at http://pubs.acs.org.
C
60, 60 mL of chlorobenzene, and 0.038 g (0.05 mmol) of
complex 2 were used. The product was separated by TLC using
1/2 (v/v) toluene/light petroleum ether as eluent under anaero-
bic conditions. The first band gave a small amount of C60. From
the chlorophyll green band was obtained 0.052 g (66%) of 4 as
OM990975W