Synthesis and characterization of group 6 transition-metal [70]fullerene derivatives containing dppb ligands. Crystal structure of fac-Mo(CO)3(dppb)(CH3CN)

Article abstract of DOI:10.1016/S0022-328X(02)01876-4

The thermal reaction of an equimolar quantity of fac-Mo(CO)₃(dppb)(CH₃CN) [dppb = 1,2-bis(diphenylphosphino)benzene] (1) with C₇₀ in chlorobenzene at 80-85 C gave an isomeric mixture of fac/mer-Mo(CO)₃(dppb)(η

Full text of DOI:10.1016/S0022-328X(02)01876-4

Journal of Organometallic Chemistry 662 (2002) 51ꢁ58
/
www.elsevier.com/locate/jorganchem
Synthesis and characterization of Group 6 transition-metal
[70]fullerene derivatives containing dppb ligands.
Crystal structure of fac-Mo(CO)3(dppb)(CH3CN)
Li-Cheng Song *, Jin-Ting Liu, Qing-Mei Hu
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, PR China
Received 28 May 2002; received in revised form 1 August 2002; accepted 31 August 2002
Abstract
The thermal reaction of an equimolar quantity of fac-Mo(CO)3(dppb)(CH3CN) [dppbꢀ
/
1,2-bis(diphenylphosphino)benzene] (1)
with C70 in chlorobenzene at 80ꢁ
/
85 8C gave an isomeric mixture of fac/mer-Mo(CO)3(dppb)(h2-C70) (2) in 46% yield, whereas the
photochemical reaction of an equimolar amount of Mo(CO)6, dppb and C70 in chlorobenzene at room temperature afforded the
isomeric mixture 2 in 48% yield and a single isomer mer-[Mo(CO)3 (dppb)]2(h2,h2-C70) (3) in 19% yield. Similarly, while the thermal
reaction of fac-W(CO)3 (dppb)(CH3CN) (4) with C70 produced a single isomer mer-W(CO)3(dppb) (h2-C70) (5) in 42% yield, the
photochemical ‘one pot’ reaction of Cr(CO)6, dppb and C70 gave rise to a single isomer mer-Cr(CO)3(dppb)(h2-C70) (6) in 62% yield
and a single isomer [mer-Cr(CO)3(dppb)]2(h2,h2-C70) (7) in 25% yield, respectively. All the new [70]fullerene mono- and dinuclear
organometallic derivatives 2, 3 and 5ꢁ
/
7 have been characterized by elemental analysis, and IR, 1H-, 31P-, 13C-NMR (partly), UVꢁ
/
vis and FAB-MS spectroscopic methods, as well as the crystal structure of one of their starting materials fac-
Mo(CO)3(dppb)(CH3CN) (1) has been determined by X-ray diffraction analysis.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Chromium; Molybdenum; Tungsten; [70]Fullerene; dppb Ligand; Crystal structures
1. Introduction
transition-metals in the Periodic Table [2ꢁ5]. In contrast
/
to this, the known [70]fullerene transition-metal com-
plexes are rare and only limited to few metals, which is
apparently due to less abundant of [70]fullerene and the
complexes of [70]fullerene being more difficult to be
isolated and characterized than those of [60]fullerene
The organometallic chemistry of [60]- and [70]full-
erenes, primarily including the synthesis, structural
characterization and properties of transition-metal
[60]- and [70]fullerenes is of great interest and has
become one of the most active research areas in
chemistry [1]. Theoretically, [60]- and [70]fullerenes can
form organometallic compounds with single, double,
triple or multiple metal centers in a variety of coordina-
tion patterns from h1 to h6. In fact, some of these types
of transition-metal fullerene derivatives have been
[2aꢁc,2n,3b,5c,5f]. In order to develop the organome-
/
tallic chemistry of [70]fullerene, we recently carried out
the thermal reaction of fac-M(CO)3(dppb)(CH3CN)
(Mꢀ/Mo, W) with C70, and the photochemical reaction
of M(CO)6 (Mꢀ/Cr, Mo), dppb and C70. Herein we
describe the synthesis, characterization and properties of
five new mono- and dinuclear [70]fullerene complexes
obtained from the reactions mentioned above, namely,
already prepared and structurally characterized [2ꢁ5].
/
However, among such known fullerene metal complexes
an overwhelming majority belongs to [60]fullerene
derivatives, which actually involve nearly all of the
fac/mer-Mo(CO)3(dppb)(h2-C70),
[mer-Mo(CO)3-
(dppb)]2(h2,h2-C70), mer-W(CO)3(dppb)(h2-C70), mer-
Cr(CO)3(dppb)(h2-C70) and [mer-Cr(CO)3(dppb)]2(h2,
h2-C70), as well as the crystal structure of fac-
Mo(CO)3(dppb)(CH3CN), which is the precursor of
fac/mer-Mo(CO)3(dppb)(h2-C70).
* Corresponding author. Fax: ꢂ
/
86-22-23504853
E-mail address: lesong@public.tpt.tj.cn (L.-C. Song).
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 8 7 6 - 4

52
L.-C. Song et al. / Journal of Organometallic Chemistry 662 (2002) 51ꢁ58
/
2. Results and discussion
2.1. Synthesis and characterization of fac/mer-
Mo(CO)3(dppb)(h2-C70) (2) and [mer-
Mo(CO)3(dppb)]2(h2,h2-C70) (3)
Reaction of an equimolar amount of fac-
Mo(CO)3(dppb)(CH3CN) (1) with C70 in chlorobenzene
at 80ꢁ
/
85 8C for 6 h gave an isomeric mixture 2 in 46%
yield, as shown in Eq. (1).
Fig. 1. 31P-NMR spectrum of 2.
Compounds 2 and 3 are air-stable, brown solids,
which dissolve in benzene, toluene, THF, CHCl3, CS2
and chlorobenzene, but do not dissolve in hexane and
petroleum ether. Compounds 2 and 3 have been
characterized by elemental analysis and spectroscopic
methods.
ð1Þ
The 31P-NMR spectrum of 2 (Fig. 1) shows two
apparent singlets (the JPÃP values are too small to be
recognized as two doublets) at 57.56 and 63.70 ppm for
the two different P atoms cis and trans to C70,
respectively in the mer-isomer and one singlet at 60.68
ppm for the two identical P atoms all cis to C70 core in
the fac-isomer, whereas that of 3 (Fig. 2) displays one
singlet at 62.48 ppm and one singlet at 70.04 ppm for the
two types of P atoms, in which the one type of P atoms
including two identical P atoms cis to C70 and the other
type of P atoms including another two identical P atoms
trans to C70 core in the mer-isomer [2q,3h]. The IR
spectra of 2 and 3 display six absorption bands in the
The formation of the fac/mer isomeric mixture 2
means that the substitution of CH3CN by C70 took
place with partial conversion of the fac configuration of
the starting material 1 under the studied conditions.
More interestingly, when a mixture of an equimolar
quantity of Mo(CO)6, dppb and C70 in chlorobenzene
was irradiated with a UV 450 W photochemical lamp at
room temperature for 2 h, the fac/mer-isomer mixture 2
was produced in 48% yield along with mer-isomer 3 in
19% yield, as shown in Eq. (2).
range 1431ꢁ
(for 2) or three (for 3) absorption bands in the region
2023ꢁ
1893 cmꢃ1 for their terminal carbonyls [7]. The
/
525 cmꢃ1 for their C70 cores [6], and five
ð2Þ
/
number of IR bands caused by CO’s of 2 and 3 is in
We previously reported that the [60]fullerene dppf
analogue of 2, i.e. fac/mer-Mo(CO)3(dppf)(h2-C60)
[dppfꢀ1,1?-bis(diphenylphosphino)ferrocene] can be
/
prepared by CO substitution of Mo(CO)4(dppf) with
C60 [3h]. So, the [70]fullerene dppb derivatives 2 and 3
obtained from the one pot reaction described above
could be regarded as produced via the substitution of
one CO ligand from one molecule of the intermediate
Mo(CO)4(dppb) (generated in situ from Mo(CO)6 and
dppb) by C70 and the substitution of two CO ligands
each from one molecule of the intermediate by C70,
respectively.
Fig. 2. 31P-NMR spectrum of 3.

L.-C. Song et al. / Journal of Organometallic Chemistry 662 (2002) 51ꢁ
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53
good agreement with 2 being a fac/mer isomeric mixture
and 3 being a mer-isomer, since the number of IR active
bands cannot exceed but may be less than the number of
CO ligands in transition-metal complexes [7]. In addi-
tion, such IR bands of 2 and 3, when compared to
corresponding those of 1, are shifted toward higher
frequency, which is obviously due to C70 being a
stronger electron-withdrawing ligand than CH3CN and
therefore causing the decrease in the p-back-bonding
Mo atom through one CaÃ
/
Cb bond at the pole of C70
ligand. It is also known [1d,2a,2k,3b] that when a second
metal is bonded to C70 core the metal is also attached to
the CaÃ/Cb bond which is located at opposite pole of the
C70 core, presumably due to the electronic and steric
effects between the two transition-metal moieties. In
fact, at the opposite pole of C70 core there are three
distinct CaÃ
site A is closest to the first metal, the CaÃ
intermediate and the CaÃCb at site C is farthest. It
appears that in compound 3 the second metal moiety
Mo(CO)3(dppb) is most likely to be bonded at the CaÃ
Cb bond of site B, although the addition of
Mo(CO)3(dppb) to CaÃCb bonds at sites A and C
cannot be completely ruled out. This is because that the
X-ray diffraction has revealed that in
(C70)[Ir(CO)Cl(PPhMe2)2]2×3C6H6 the second Ir-con-
taining fragment is added to the CaÃCb of site B [3b].
/
Cb bonds (Fig. 3), of which the CaÃ
/
Cb at
/
Cb at site B is
/
between MoÃ
/
CO in 2 and 3 [3h,7]. The UVꢁvis
/
spectrum of 2 showing five absorption bands between
200 and 500 nm is very similar to that of free C70 [6]. In
order to make an accurate comparion, we determined
/
/
the UVꢁvis spectrum of free C70 in its saturated THF
/
solution (lmax (log o): 240.5 (5.14), 331.1 (4.53), 359.5
(4.43), 378.5 (4.57), 470.1 (4.32) nm). The blue-shift of
the fifth band of 2 relative to that of free C70 might be
ascribed to the [70]fullerene being coordinated to the
metals in an h2-fashion [2i,2q,8].
/
/
However, the exact structure of 3 remains to be solved in
the future by X-ray diffraction analysis.
In addition, the 13C-NMR spectrum of 2 shows the
presence of its terminal carbonyls (three signals from
217.98 to 209.89 ppm) and the C70 core (six signals from
150.36 to 145.08 ppm along with the others overlapped
with those of benzene rings).
Additionally, it should be pointed out that the
elemental analysis and the FAB-MS data are also
consistent with the mononuclear and dinuclear struc-
tures of 2 and 3 discussed above. For instance, the FAB-
MS spectra show the molecular ion [Mꢂ] peaks at m/
It is known [1d,2a,2k,3b] that the C70 molecule has
zꢀ
/
1468 for 2 and m/zꢀ2096 for 3, respectively.
/
five types of carbon atoms (labeled aꢁe in Fig. 3) that
/
form nine layers and display five 13C-NMR signals
(150.07, 147.52, 146.82, 144.77 and 130.28 ppm). Con-
2.2. Crystal structure of fac-M(CO)3(dppb)(CH3CN)
(1)
necting these carbon atoms are eight types of CÃ
bonds. Of these bonds four (CaÃCb, CcÃCc, CdÃCe,
CeÃCe) occurs between 6:6 ring junctions, and four
(CaÃCa, CbÃCc, CcÃCd, CdÃCd) involve 6:5 ring
junctions. The CÃC bond lengths at the 6:6 ring
junctions are shorter than the CÃC bond lengths at
the 6:5 ring junctions. The most reactive bonds are
expected to be the CaÃCb bonds at the poles of the
/C
/
/
/
/
Although the crystal structures of the [70]fullerene
derivatives 2 and 3 failed to be determined due to lack of
the single crystals suitable for X-ray diffraction, we have
successfully determined the crystal structure of their
parent complex 1 by means of X-ray diffraction
techniques. The single crystals were obtained through
slow cooling the hot CH3CN solution of 1. It should be
noted [2q] that although the structure of 1 was
previously characterized by combustion analysis and
spectroscopic methods, it could not be confirmed by X-
ray diffraction analysis due to lack of suitable single
/
/
/
/
/
/
/
molecule since they have the highest p bond orders and
the greatest cuvature [1d,2a,2k,3b]. In fact, that C70 is
bound to a metal in an h2-fashion with CaÃ
/Cb bond has
been confirmed by X-ray diffraction analysis for the
known C70 metal complexes, such as Ir(CO)(Cl)-
(PPh3)2(h2-C70) [2a] and mer-Mo(CO)3(dppe)(h2-C70)
[2k]. So, in product 2 the C70 is most likely bonded to
Fig. 3. The idealized structure of C70 and sites for the first and second
metal moieties added to C70 [1d].
Fig. 4. ORTEP drawing of 1 with ellipsoids drawn at 30% probability.

54
L.-C. Song et al. / Journal of Organometallic Chemistry 662 (2002) 51ꢁ58
/
Table 1
˚
Selected bond lengths (A) and angles (8) for fac-
Mo(CO)3(dppb)(CH3CN) (1)
Bond lengths
Mo(1)ÃC(1)
Mo(1)ÃC(2)
Mo(1)ÃN(1)
Mo(1)ÃP(2)
C(11)ÃP(2)
1.933(8)
1.970(9)
2.217(7)
Mo(1)ÃP(1)
P(1)ÃC(16)
P(1)ÃC(31)
2.497(2)
1.826(7)
1.819(7)
1.813(7)
1.125(8)
ð3Þ
2.4902(19) P(2)ÃC(41)
1.836(7)
So, in contrast to reaction of 1 with C70, this reaction
did not afford the corresponding fac/mer isomeric
mixture, but instead it produced only the mer-isomer
5, which means that the substitution of CH3CN by C70
occurred in this case with complete conversion of the fac
configuration of starting material 4.
N(1)ÃC(4)
Bond angles
C(1)ÃMo(1)ÃN(1)
P(1)ÃMo(1)ÃC(1)
N(1)ÃMo(1)ÃP(1)
C(41)ÃP(2)ÃMo(1) 113.8(2)
C(31)ÃP(1)ÃMo(1) 121.0(2)
179.0(3)
96.0(2)
C(1)ÃMo(1)ÃP(2)
N(1)ÃMo(1)ÃP(2)
94.5(2)
84.64(16)
79.73(6)
110.8(2)
114.8(2)
177.2(9)
84.43(16) P(2)ÃMo(1)ÃP(1)
C(11)ÃP(2)ÃMo(1)
C(21)ÃP(1)ÃMo(1)
N(1)ÃC(4)ÃC(5)
Compound 5 is an air-stable, black solid, which is
soluble in benzene, toluene, THF, CHCl3, CS2 and
chlorobenzene, but is insoluble in hexane and petroleum
ether. Compound 5 has been characterized by elemental
C(4)ÃN(1)ÃMo(1)
172.8(6)
analysis IR, UVꢁ
techniques. For example, the FAB-MS spectrum shows
its molecular ion peak at m/zꢀ
1556 and Cꢂ70 ion peak.
The UVꢁvis spectrum of 5 is similar to that of free C70,
/
vis, 1H-, 31P-NMR and FAB-MS
crystals during that time. The molecular ORTEP diagram
of 1 is shown in Fig. 4, whereas Table 1 lists its selected
bond lengths and angles.
Fig. 4 shows that 1 contains one CH3CN ligand
bonded to Mo via its N atom and cis to both of the
phosphorous atoms P(1) and P(2) of the dppb ligand.
That is, the X-ray diffraction analysis confirmed that 1
adopts the fac configuration, indeed. This molecule is
symmetrical with respect to the plane passing through
N(1), Mo(1) and C(1) atoms, and the midpoints of
/
/
in which the fifth band at 460.9 nm, characteristic of an
h2-coordinating fashion of C70 with the metal, is blue-
shifted by ca. 9 nm relative to that of free C70 [2i,2q,8].
The IR spectrum of 5 displays four bands in the region
1430ꢁ
/
525 cmꢃ1 for its C70 core [6] and three bands in
1886 cmꢃ1 for its terminal carbonyls [7].
the range 2009ꢁ
/
In addition, the 31P-NMR spectrum of 5 shows two
broader singlets centered at 43.40 and 38.90 ppm, each
singlet being surrounded by satellite peaks due to
coupling between P atoms and tungsten isotopes, such
as isotope 183W. This indicates that it has two different P
atoms, and thus 5 is a single mer-isomer [2q,3h].
According to the above discussion regarding the metal
position bonded to C70 core, we might suggest that in
the mer-isomer 5 the metal tungsten is just like the Mo
atoms in mer-isomers 2 and 3 to be bonded to C70 core
C(11)Ã
/
C(16) and C(13)Ã
/
C(14) bonds. The chelated
Mo(1)ÃP(2)
dppb ligand has a bite angle of P(1)Ã
/
/
(79.73(6)8), which is greater than corresponding that of
fac-W(CO)3(dppm)(CH3CN) (67.5(1)8) [9], but less than
corresponding those of fac-Mo(CO)3(dppf)(CH3CN)
(97.80(19)8)
(98.05(6)8) [10], Mo(CO)4(dppf) (95.28(2)8) [11],
W(CO)4(dppf) (95.24(5)8) [3h]. The two MoÃP, and
one MoÃN bond lengths of 1 are 2.497(2) (Mo(1)ÃP(1)),
2.4902(19) (Mo(1)ÃP(2)) and 2.217(7) (Mo(1)ÃN(1)) A,
whereas the three MoÃC(carbonyl) bond lengths in 1
are 1.933(8) (Mo(1)ÃC(1)), 1.970(9) (Mo(1)ÃC(2)) and
C(3)) A, respectively. That the Mo(1)Ã
C(1) bond is the shortest among the three MoÃ
[3h],
fac-W(CO)3(dppf)(CH3CN)
/
/
/
˚
/
/
through its CaÃ
/
Cb bond [1d,2a,2k,3b].
/
/
/
˚
1.965(8) (Mo(1)Ã
/
/
2.4. Synthesis and characterization of mer-
Cr(CO)3(dppb)(h2-C70) (6) and [mer-
Cr(CO)3(dppb)]2(h2,h2-C70) (7)
/
C(carbonyl) bonds implies that acetonitrile possesses a
weaker trans effect than dppb and this is consistent with
CH3CN being a weaker ligand and being more easily
replaced by C70 to give fullerene derivative 2.
Although the Mo and W organometallics of [70]full-
erene are known [2k,3h] none of the corresponding Cr
derivatives has appeared in literature until now. So, the
efforts were made to synthesize the Cr analogues of 2, 3
and 5. Fortunately, while the Cr analogue 6 could not be
prepared by reaction of fac-Cr(CO)3(dppb)(CH3CN)
with C70 under the above-mentioned thermal reaction
conditions, the Cr analogues 6 and 7 were obtained,
respectively in 62 and 25% yields through photochemical
reaction of a mixture of Cr(CO)6, dppb and C70, as
shown in Eq. (4).
2.3. Synthesis and characterization of mer-
W(CO)3(dppb)(h2-C70) (5)
Interestingly, an equimolar quantity of fac-
W(CO)3(dppb)(CH3CN) (4) reacted with C70 in chlor-
obenzene at 80ꢁ
shown in Eq. (3).
/
85 8C for 6 h to give 5 in 42% yield, as

L.-C. Song et al. / Journal of Organometallic Chemistry 662 (2002) 51ꢁ
/58
55
metallic fullerene complexes and it would be very useful
in preparation of other novel fullerene organometallic
compounds. Finally, it is worth pointing out that
although the [70]fullerene transition-metal complexes
are known (but very few), the complexes 6 and 7
reported in this paper, to our best knowledge, are the
first examples of the [70]fullerene organometallic com-
plexes in which the [70]fullerene is coordinated to
transition-metal chromium.
ð4Þ
Compounds 6 and 7 are air-sensitive, brown solids,
which are, similar to 2, 3 and 5, soluble in benzene,
toluene, THF, CHCl3, CS2 and chlorobenzene, but are
insoluble in hexane and petroleum ether. The structures
3. Experimental
All reactions were carried out under an atmosphere of
highly purified nitrogen using standard Schlenk or
vacuum-line techniques. Acetonitrile and chlorobenzene
were dried by distillation from P2O5 and CaH2 under
nitrogen. M(CO)6 (Mꢀ
sphino)benzene (dppb) and [70]fullerene (98%) were of
commercial origin. M(CO)3(dppb)(CH3CN) (Mꢀ
Mo,W) [2n] were prepared according to literature
procedures. Products were separated by thin-layer
chromatography (TLC glass plates of 20ꢄ
of 6 and 7 shown in Eq. (4) have been characterized by
1
elmental analysis, IR, UVꢁ
FAB-MS methods.
The FAB-MS spectrum of 6 exhibits its molecular ion
[Mꢂ] at m/zꢀ1424 and fragment ions [Mꢂꢃ
3CO] and
Cꢂ70; whereas that of 7 displays the peaks corresponding
to its [Mꢂꢃ 2005, [Mꢂꢃ3CO], [Mꢂꢃ
3H] at m/zꢀ
6CO] and Cꢂ70: The IR spectra of 6 and 7 each show
three absorption bands in the range 2008ꢁ
1884 cmꢃ1
for their terminal carbonyls [7], and three to four
absorption bands in the region 1434ꢁ
527 cmꢃ1 for its
/
vis, H(13C, 31P)-NMR, and
/
Cr, Mo), 1,2-bis(diphenylpho-
/
/
/
/
/
/
/
/
25ꢄ0.25
/
/
cm coated with silica gel 60H). M.p. were determined on
a Yanaco MP-500 apparatus. Elemental analysis and
FAB-MS spectrometry were performed on a Yanaco
CHN Corder MT-3 analyzer and a Zebspec spectro-
/
1
C70 core [6], whereas the H-NMR spectra of 6 and 7
display all of their corresponding organic groups. The
13C-NMR spectrum of 6, similar to that of 2, also shows
its terminal carbonyls (three signals from 226.54 to
225.89 ppm) and the C70 core (six signals from 150.79 to
136.49 ppm along with the others overlapped with those
from C6H5 and C6H4 groups). It is worthy of note that
the 31P-NMR spectrum of 6 displays two singlets at
93.66 and 82.45 ppm for its two different P atoms,
whereas that of 7 shows two doublets at 95.23 and 82.94
ppm for its two sets of two different P atoms [2q,3h]. So,
it seems that the structures of 6 and 7 are very similar to
5 and 3 resepctively, i.e. they all belong to mer-isomers
in which the first Cr(CO)3(dppb) moiety is presumably
meter. IR and UVꢁvis spectra were recorded on a Bio-
/
Rad FTS 135 and a Shimadzu UV-2401/PC spectro-
1
meters. H-, 31P- and 13C-NMR spectra were obtained
on a Bruker AC-P200 or a UNITY Plus-400 spectro-
meter.
3.1. Synthesis of fac/mer-Mo(CO)3(dppb)(h2-C70) (2)
A 100-ml three-necked flask equipped with a stir-bar,
a serum cap and a reflux condenser topped with a N2
inlet tube was charged with 0.042 g (0.05 mmol) of C70
and 50 ml of chlorobenzene. The mixture was stirred at
room temperature (r.t.) until all C70 was dissolved. To
the brown solution was added 0.033 g (0.05 mmol) of
Mo(CO)3(dppb)(CH3CN), and the reaction mixture was
bonded via Cr atom to the CaÃ
/
Cb bond of C70 core and
the second Cr(CO)3(dppb) moiety is bound to the CaÃ
/
Cb bond at the opposite pole of the C70 core
[1d,2a,2k,3b].
In summary, we have synthesized a series of new
organometallic [70]fullerene compounds by use of
thermal reaction of fac-M(CO)3(dppb)(CH3CN) (M
heated to about 80 8C and stirred at 80ꢁ85 8C for 6 h,
/
during which time the solution turned dark brown. The
resulting solution was evaporated at reduced pressure,
and the residue was separated by TLC using 1:1 (v/v)
C6H5CH3ꢁ
yellowꢁgreen band 0.034 g (46%) of 2 as a brown solid
was obtained. m.p. ꢀ300 8C. Anal. Found: C, 84.68;
/light petroleum ether as eluent. From the
ꢀ/Mo, W) with C70, and photochemical reaction of
/
M(CO)6 (MꢀCr, Mo), dppb and C70. Interestingly,
/
/
while the thermal reaction gives mononuclear [70]full-
erene complexes 2 and 5, the photochemical reaction
affords both mononuclear and dinuclear [70]fullerene
complexes 2/3 and 6/7. So far, the photochemical ‘one
pot’ reaction, which was first carried out in our
laboratory, is probably the most simple and straightfor-
ward reaction for preparation of such types of organo-
H, 1.51. Calc. for C103H24MoO3P2: C, 84.32; H, 1.65%.
IR (KBr disc): nCÅO, 2023m, 2021s, 1951s, 1924s,
1896vs; nC70 1431s, 795w, 673w, 641w, 579w, 525m
cmꢃ1. UVꢁ
/
vis (THF, 8.36ꢄ
10ꢃ6 M): lmax (log o):
239.9 (5.30), 329.3 (4.57), 357.7 (4.57), 378.3 (4.55),
/
1
464.1 (4.43) nm. H-NMR (200 MHz, CDCl3, Me4Si):
7.24ꢁ
7.45 (m, 24H, 4C6H5, C6H4) ppm. 13C-NMR
/

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L.-C. Song et al. / Journal of Organometallic Chemistry 662 (2002) 51ꢁ58
/
(100.6 MHz, o-C6D4Cl2, Me4Si, 25 8C): 3 multiplets
centered at 217.98, 210.81 and 209.89 (CO), 6 singlets at
150.36, 148.09, 147.83, 147.37, 147.12 and 145.08 (C70),
15 singlets at 134.24, 133.56, 133.31, 132.76, 132.51,
131.07, 130.85, 130.61, 129.62, 129.37, 128.42, 127.74,
3.4. Synthesis of mer-Cr(CO)3(dppb)(h2-C70) (6) and
[mer-Cr(CO)3(dppb)]2(h2,h2-C70) (7)
The same procedure as that for preparation of 2 and 3
by photochemical reaction was followed, but 0.042 g
(0.05 mmol) of C70, 0.016 g (0.075 mmol) of Cr(CO)6
and 0.034 g (0.075 mmol) of dppb were employed. From
127.49, 127.24 and 126.99 (C70ꢂ
/
Phꢂ
/
C6H4ꢂo-
/
C6D4Cl2) ppm. 31P-NMR (81 MHz, o-C6D4Cl2,
H3PO4): 63.70 (s, 1P), 57.56 (s, 1P), 60.68 (s, 2P) ppm.
FAB-MS: m/z 1468 (Mo(CO)3(dppb) (h2-C70)ꢂ, 98Mo);
the yellowꢁ/green band 0.044 g (62%) of 6 as a brown
solid was obtained. m.p. ꢀ
/
300 8C. Anal. Found: C,
m/z 840 (
/
Cꢂ70):
/
87.02; H, 1.66. Calc. for C103H24CrO3P2: C, 86.92; H,
1.70%. IR (KBr disc): nCÅO, 2008s, 1917vs, 1890vs; nC70
1432s, 793w, 675m, 528s cmꢃ1. UVꢁ
/
vis (THF, 9.56ꢄ
10ꢃ6 M) lmax (log o): 239.3 (5.18), 378.0 (4.40), 469.1
(4.41) nm. 1H-NMR (200 MHz, CS2ꢁ
C3H6O-d6,
Me4Si): 7.10ꢁ
7.70 (m, 48H, 8C6H5, 2C6H4) ppm. 13C-
/
3.2. Synthesis of 2 and [mer-Mo(CO)3(dppb)]2(h2,h2-
C70) (3)
/
/
NMR (100.6 MHz, CDCl3, Me4Si, 25 8C): 3 broad
singlets centered at 226.54, 226.23 and 225.89 (CO), 6
singlets at 150.79, 148.23, 147.53, 145.48, 143.33 and
136.49 (C70), 8 singlets at 132.32, 131.02, 130.43, 129.86,
A 100-ml photoreactor equipped with a N2 inlet tube
and a serum cap was charged with 0.042 g (0.05 mmol)
of C70, 0.014 g (0.05 mmol) of Mo(CO)6, 0.023 g (0.05
mmol) of dppb and 50 ml of chlorobenzene. The
photoreactor containing the resulting brown solution
was evacuated to a pressure of ca. 0.1 mmHg and then
the solution was irradiated by a water-cooled UV 450 W
mercury vapor lamp for 2 h, with periodic evacuation of
CO to give a dark brown solution. The same work-up
was used as that in preparation of 2 by thermal reaction.
129.25, 128.58, 123.93 and 120.55 (C70ꢂ
/
PhꢂC6H4)
/
ppm. 31P-NMR (81 MHz, CS2, H3PO4): 93.66 (s, 1P),
82.45 (s, 1P) ppm. FAB-MS: m/z 1424 (Cr(CO)3(dppb)
(h2-C70)ꢂ, 54Cr); m/z 1340 (Cr(CO)3(dppb)(h2-C70)ꢂꢃ
/
3CO, 54Cr); m/z 840 (
0.019 g (25%) of 7 was obtained as a brown solid. m.p.
300 8C. Anal. Found: C, 81.70; H, 2.42. Calc. for
136H48Cr2O6P4: C, 81.44; H, 2.41%. IR (KBr disc):
nCÅO, 1992s, 1921s, 1884vs; nC70 1434s, 670w, 527s
/
Cꢂ70): From the redꢁ
brown band
/
ꢀ
/
From the yellowꢁ
obtained. From the redꢁ
as a brown solid was obtained. m.p. ꢀ
/
green band 0.035 g (48%) of 2 was
brown band 0.010 g (19%) of 3
300 8C. Anal.
C
/
/
cmꢃ1. UVꢁ
/
vis (THF, 8.97ꢄ
/
10ꢃ6 M) lmax (log o):
Found: C, 78.08; H, 2.29. Calc. for C136H48Mo2O6P4: C,
78.02; H, 2.31%. IR (KBr disc): nCÅO, 2006s, 1940s,
1893vs; nC70 1431s, 792w, 670w, 640w, 595w, 525m
Table 2
Crystal
Mo(CO)3(dppb)(CH3CN)(1)
data
and
structure
refinements
for
fac-
cmꢃ1
.
1H-NMR (200 MHz, CS2ꢁ
/
C3H6O-d6, Me4Si):
7.02ꢁ
/
7.62 (m, 48H, 8C6H5, 2C6H4) ppm. 31P-NMR (81
MHz, CS2, H3PO4): 70.04 (s, 2P), 62.48 (br.s, 2P) ppm.
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C35H27MoNO3P2
667.46
293
P21/c
FAB-MS: m/z 2096 ([Mo(CO)3(dppb)]2 (h2,h2-C70)ꢂ,
98Mo); m/z 840 (
/
Cꢂ70):
/
Monoclinic
8.4759(16)
16.792(3)
22.110(4)
90
˚
a (A)
˚
b (A)
3.3. Synthesis of mer-W(CO)3(dppb)(h2-C70) (5)
˚
c (A)
a (8)
b (8)
98.864(4)
90
The same procedure as that for preparation of 2 by
thermal reaction was followed, but 0.038 g (0.05 mmol)
of fac-W(CO)3(dppb)(CH3CN) was used instead of fac-
g (8)
3
V (A )
˚
3109.3(10)
4
1.426
Z
Dcalc (g cmꢃ3
)
Mo(CO)3(dppb)(CH3CN). From the yellowꢁ
0.037 g (42%) of 5 as a black solid was obtained. m.p. ꢀ
300 8C. Anal. Found: C, 79.56; H, 1.51. Calc. for
103H24O3P2W: C, 79.55; H, 1.56%. IR (KBr disc):
nCÅO, 2009s, 1943s, 1886vs; nC70 1430s, 671w, 536m,
525m cmꢃ1. UVꢁ 10ꢃ5 M): lmax
vis (THF, 1.50ꢄ
/
green band
m(Moꢁ
/
Ka) (mmꢃ1
)
0.560
1360
/
F(000)
u Range for data collection (8)
Observed reflections
Independent reflections
Rint
2.43ꢁ25.03
11715
5063
/
C
/
/
0.1001
88.9%
5063/03/380
Completeness to uꢀ25.038
Data/restraints/parameters
Final R indices [I ꢀ2s(I)]
R indices (all data)
Goodness-of-fit on F2
˚
Largest difference peak and hole (e A
(log o): 241.1 (5.17), 329.3 (4.46), 357.5 (4.41), 377.9
1
(4.45), 460.9 (4.35) nm. H-NMR (200 MHz, CDCl3,
R1ꢀ0.0749, wR2ꢀ0.1448
R1ꢀ0.1404, wR2ꢀ0.1714
0.990
Me4Si): 7.10ꢁ
7.66 (m, 24H, 4C6H5, C6H4) ppm. 31P-
NMR (81 MHz, o-C6D4Cl2, H3PO4): 43.40 (s, 1P), 38.90
/
(s, 1P) ppm. FAB-MS: m/z 1556 (W(CO)3(dppb) (h2-
ꢃ3
)
0.976 and ꢃ0.429
C70)ꢂ, 186W); m/z 840 (
/
Cꢂ70):
/

L.-C. Song et al. / Journal of Organometallic Chemistry 662 (2002) 51ꢁ
/58
57
239.5 (5.25), 377.5 (4.56), 470.3 (4.59) nm. 1H-NMR
(200 MHz, CS2ꢁC3H6O-d6, Me4Si): 7.10ꢁ7.60 (m, 48H,
8C6H5, 2C6H4) ppm. 31P-NMR (81 MHz, CS2, H3PO4):
95.23 (d, Jꢀ26.4 Hz, 2P), 82.94 (d, Jꢀ21.6 Hz, 2P)
ppm. FAB-MS: m/z 2005 ([Cr(CO)3(dppb)]2 (h2,h2-
C70)ꢂꢃ3H, 54Cr); m/z 1921 ([Cr(CO)3(dppb)]2(h2,h2-
C70)ꢂꢃ 54Cr);
3Hꢃ3CO, m/z 1837
[{Cr(CO)3(dppb)}2(h2,h2-C70)ꢂꢃ 6CO, 54Cr]; m/
z 840 (
Cꢂ70):
[2] For mononuclear fullerene derivatives, see: (a) A.L. Balch, V.J.
Catalano, J.W. Lee, M.M. Olmstead, S.R. Parkin, J. Am. Chem.
Soc. 113 (1991) 8953;
/
/
(b) M.M. Olmstead, L. Hao, A.L. Balch, J. Organomet. Chem.
578 (1999) 85;
/
/
(c) A.V. Usatov, K.N. Kudin, E.V. Vorontsov, L.E. Vinogradova,
Y.N. Novikov, J. Organomet. Chem. 522 (1996) 147;
(d) A.L. Balch, V.J. Catalano, J.W. Lee, M.M. Olmstead, J. Am.
Chem. Soc. 114 (1992) 5455;
/
/
/
/
3Hꢃ
/
(e) V.V. Bashilov, P.V. Petrovskii, V.I. Sokolov, S.V. Lindeman,
I.A. Guzey, Y.T. Struchkov, Organometallics 12 (1993) 991;
(f) M. Sawamura, H. Iikura, E. Nakamura, J. Am. Chem. Soc.
118 (1996) 12850;
/
/
3.5. X-ray crystallography
(g) K. Tang, S. Zheng, X. Jin, Z. Gu, X. Zhou, Y. Tang, J. Chem.
Soc. Dalton Trans. (1997) 3585;
Single crystals of fac-Mo(CO)3(dppb)(CH3CN) (1)
suitable for X-ray diffraction analysis were obtained by
slow cooling the hot MeCN solution of 1. The single
(h) M.V. Wijnkoop, M.F. Meidine, A.G. Avent, A.D. Darwish,
H.W. Kroto, R. Taylor, D.R.M. Walton, J. Chem. Soc. Dalton
Trans. (1997) 675;
(i) A.N. Chernega, M.L.H. Green, J. Haggitt, A.H.H. Stephens, J.
Chem. Soc. Dalton Trans. (1998) 755;
crystal of 1 (0.20ꢄ
/
0.20ꢄ0.15 mm) was glued to a glass
/
fiber and mounted on a Bruker SMART 1000 auto-
mated diffractometer. Data were collected at r.t., using
(j) H. Maruyama, M. Fujiwara, K. Tanaka, Chem. Lett. (1998)
805;
(k) H.-F. Hsu, Y. Du, T.E. Albrecht-Schmitt, S.R.Wilson, J.R.
Shapley, Organometallics 17 (1998) 1756;
Moꢁ
/
Ka graphite monochromator radiation (lꢀ
/
˚
0.71073 A) in the v scanning mode. Absorption
corrections were performed using SADABS for all of
them. The structure was solved by direct methods using
SHELXTL-97 program and refined by full-matrix least-
squares techniques (SHELXL-97) on F2. Hydrogen atoms
were located by using geometric method. The crystal
data and structural refinements details are listed in
Table 2.
(l) M.N. Bengough, D.M. Thompson, M.C. Baird, Organome-
tallics 18 (1999) 2950;
(m) L.-C. Song, Y.-H. Zhu, Q.-M. Hu, Polyhedron 16 (1997)
2141;
(n) L.-C. Song, Y.-H. Zhu, Q.-M. Hu, Polyhedron 17 (1998) 469;
(o) Y.-L. Song, G.-Y. Fang, Y.-X. Wang, C.-F. Liu, L.-C. Song,
Y.-H. Zhu, Q.-M. Hu, Appl. Phys. Lett. 74 (1999) 1;
(p) L.-C. Song, Y.-H. Zhu, Q.-M. Hu, J. Chem. Res. Synop.
(1999) 56;
(q) L.-C. Song, J.-T. Liu, Q.-M. Hu, L.-H. Weng, Organome-
tallics 19 (2000) 1643.
[3] For dinuclear fullerene derivatives, see: (a) A.L. Balch, J.W. Lee,
B.C. Noll, M.M. Olmstead, J. Am. Chem. Soc. 114 (1992) 10984;
(b) A.L. Balch, J.W. Lee, M.M. Olmstead, Angew. Chem. Int. Ed.
Engl. 31 (1992) 1356;
4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 185862 for compound 1.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
(c) S. Zhang, T.L. Brown, Y. Du, J.R. Shapley, J. Am. Chem.
Soc. 115 (1993) 6705;
(d) A.L. Balch, J.W. Lee, B.C. Noll, M.M. Olmstead, Inorg.
Chem. 33 (1994) 5238;
(e) I.J. Mavunkal, Y. Chi, S.-M. Peng, G.-H. Lee, Organome-
tallics 14 (1995) 4454;
Cambridge CB2 1EZ, UK (Fax: ꢂ44-1223-336033; e-
/
(f) Y.-H. Zhu, L.-C. Song, Q.-H. Hu, C.-M. Li, Org. Lett. 1
(1999) 1693;
mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
(g) L.-C. Song, Y.-H. Zhu, Q.-M. Hu, J. Chem. Res. Synop.
(2000) 316;
(h) L.-C. Song, J.-T. Liu, Q.-M. Hu, G.-F. Wang, P. Zanello, M.
Fontani, Organometallics 19 (2000) 5342.
Acknowledgements
[4] For trinuclear fullerene derivatives, see: (a) H.-F. Hsu, J.R.
Shapley, J. Am. Chem. Soc. 118 (1996) 9192;
(b) H.-F. Hsu, J.R. Shapley, J. Chem. Soc. Chem. Commun.
(1997) 1125;
We are grateful to the National Natural Science
Foundation of China and the Laboratory of Organo-
metallic Chemistry for financial support.
(c) J.T. Park, H. Song, J.-J. Cho, M.-K. Chung, J.-H. Lee, I.-H.
Suh, Organometallics 17 (1998) 227;
(d) H. Song, K. Lee, J.T. Park, M.-G. Choi, Organometallics 17
(1998) 4477.
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