Reactions of carbanions of bis(dialkoxyphosphoryl)bromomethane with fullerenes C60 and C70

Article abstract of DOI:10.1023/A:1015472114103

The reactions of carbanions of bis(dialkoxyphosphoryl)bromomethanes with fullerenes C60 and C70 afforded new bis(dialkoxyphosphoryl)methanofullerenes C60 and C70, respectively, whose structures were established by spectroscopic methods.

Full text of DOI:10.1023/A:1015472114103

Russian Chemical Bulletin, International Edition, Vol. 51, No. 2, pp. 337—341, February, 2002
337
Reactions of carbanions of bis(dialkoxyphosphoryl)bromomethane
with fullerenes C60 and C70

I. A. Nuretdinov, V. P. Gubskaya, N. I. Shishikina, G. M. Fazleeva,
L. Sh. Berezhnaya, I. P. Karaseva, F. G. Sibgatullina, and V. V. Zverev
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843 2) 75 2253. Eꢀmail: in@iopc.kcn.ru
The reactions of carbanions of bis(dialkoxyphosphoryl)bromomethanes with fullerenes C60
and C70 afforded new bis(dialkoxyphosphoryl)methanofullerenes C60 and C70, respectively,
whose structures were established by spectroscopic methods.
Key words: bis(dialkoxyphosphoryl)bromomethanes, fullerenes C60 and C70, methanoꢀ
1
fullerenes, UV and IR spectra, H, 13C, and 31P NMR spectra, the Bingel reaction, quantumꢀ
chemical calculations, PM3 method.
Scheme 1
The chemistry of methanofullerenes have attracted
growing interest1—4 due to the fact that mild conditions of
the synthesis allow one to insert various functional groups
into the fullerene molecule thus preparing new organic
derivatives of fullerene. It should be noted that malonic
acid derivatives are generally used as the starting compoꢀ
nents in these reactions. Recently, we have described the
use of phosphonoacetate derivatives for this purpose.5—7
Previously,8 methanofullerenes containing the P atom in
the β position with respect to the 61st C atom have been
prepared. In the present study, we report the results of the
synthesis of bis(dialkoxyphosphoryl)methanofullerenes
C60 and C70. Such fullerene derivatives containing the
bis(dialkoxyphosphoryl)methane fragment can be used for
the preparation of new materials and biologically active
compounds and also as ligands in new types of metal
complex catalysts. Some results described in the present
study have been reported previously.6,7
R = Et (1), Pri (2)
generated by iodination of bis(diethoxyphosphoryl)meꢀ
thane with iodine in the presence of NaH for 9 h.
Compound 2 was formed even faster (15—20 min)
and also in high yield (∼80%). The reaction conducted
over a longer period of time gave rise to diꢀ and polyꢀ
adducts (HPLC data). Taking into account that adducts
both at the 5,6ꢀ and 6,6ꢀbonds of the fullerene core can
be formed, we calculated the heats of formation of these
compounds by the semiempirical PM3 method (the
GAMESS program package). These calculations demonꢀ
strated that the addition at the 6,6ꢀbond is energetically
more favorable than the addition at the 5,6ꢀbond (511.09
and 534.16 kcal mol–1, respectively).
The structures of the resulting compounds were studꢀ
ied by spectroscopic methods. Thus the UV spectra of
compounds 1 and 2 have absorption bands at 326, 427,
491, and 535 nm. The presence of a mediumꢀintensity
narrow absorption band at 427 nm is a simple and reliable
criterion of the formation of cycloadducts at the closed
Results and Discussion
The reactions of bis(dialkoxyphosphoryl)bromoꢀ
methanes with fullerene C60 in the presence of NaH in
toluene afforded the corresponding bis(dialkoxyphosꢀ
phoryl)methanofullerenes 1 and 2 (Scheme 1).
Bis(dialkoxyphosphoryl)bromomethanes are more reꢀ
active with respect to fullerene C60 as compared to the
known bromo(dialkoxyphosphoryl)acetates.5 At ∼20 °C,
the starting fullerene C60 was virtually completely conꢀ
sumed within 1 h after the beginning of the reaction to
give monoadduct 1 in 71% yield. It should be noted that
compound 1 has been synthesized previously9 in 38%
yield by the reaction of fullerene C60 with the product
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 317—320, February, 2002.
1066ꢀ5285/02/5102ꢀ337 $27.00 © 2002 Plenum Publishing Corporation

338
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 2, February, 2002
Nuretdinov et al.
6,6ꢀbond.1—9 The IR spectra of compounds 1 and 2 have
absorption bands at 526, 573, and 1428 cm–1 typical of
many monoadducts of fullerene C60. The 31P NMR specꢀ
tra of these compounds have singlets at δ ∼14.
phoryl)bromomethane, one must also take into considerꢀ
ation that the formation of the corresponding methanoꢀ
fullerene occurs at the 6,6ꢀbond. This is evidenced3,5 both
by the spectroscopic data and the calculated heats of forꢀ
mation of methanofullerenes at the 6,6ꢀ and 5,6ꢀbonds
(see above). Note that the molecule of fullerene C70 has
three types of nonequivalent 6,6ꢀbonds (a—b, c—c, and
d—e) due to which three products, viz., A, B, and C,
can be formed. The a—b and c—c bonds in fullerene
C70 are somewhat shorter (by ∼0.03 Å) than the
d—e bonds located closer to the equatorial region.
The molecule of fullerene C60 contains 30 equivalent
6,6ꢀbonds.
It should be noted that the 13C NMR spectra of
methanofullerenes 1 and 2 are, as expected, simpler as
compared to the spectra of nonꢀsymmetrical derivatives
of fullerene C60. Thus the 13C NMR spectra of dimethꢀ
oxyphosphoryl[61]methoxycarbonyl[61]methanofulleꢀ
rene[C60] and its ethoxy and menthyloxycarbonyl analogs
contain 25, 29, and 46 signals, respectively,5 whereas the
13C NMR spectra of compounds 1 and 2 contain only
17 signals of the fullerene core. Previously,5 we have noted
that the signal at δ 147 in the 13C NMR spectra of phosꢀ
phorylated methanofullerenes is split into a doublet.
Analogously, the 13C NMR spectra of bis(dialkoxyꢀ
phosphoryl)methanofullerenes 1 and 2 show doublets at
δ ∼147—148 (3JP,C ≈ 5.0 Hz). In the 13C NMR spectra of
compounds 1 and 2, the signals for the alkoxy groups are
observed at δ ∼15 and 17 (Me groups) and at δ ∼62 and 64
(CH2O and CHO groups), respectively. The C(61) atom
of compounds 1 and 2 gives a lowꢀintensity triplet at
δ 39.38 and 41.64 with JP,C = 151.6 Hz and JP,C
=
150.0 Hz, respectively. The signals for the sp3ꢀhybridized
C atoms of the fullerene core involved in the threeꢀmemꢀ
bered ring are observed as triplets at δ 67.46 and 69.71
with 2JP,C = 4.6 Hz and 2JP,C = 4.1 Hz, respectively.
The 1H NMR spectrum of compound 1 has signals for
the methyl (δ 1.21) and methylene (δ 4.29) protons of the
1
ethoxy groups bound to the P atom. The H NMR specꢀ
trum of compound 2 shows two doublets for the protons
of the Me groups (δ 1.32 and 1.41) and two multiplets for
the protons of the CH—O groups (δ 5.01 and 5.07).
The question as to the difference in the reactivity of
fullerenes C60 and C70 in cycloaddition was discussed in
the literature,10,11 in particular, in the studies with the use
of calculation methods. It was demonstrated that the
Diels—Alder reaction of fullerene C60 with cyclopentaꢀ
diene in toluene proceeded seven times more rapidly than
that with fullerene C70.11 However, calculations for the
reactions of fullerenes with butadiene in the gas phase
revealed that fullerene C70 is somewhat more favorable.10
It was concluded that orbital interactions are of imporꢀ
tance in these reactions, including the energies of the
lowest unoccupied MO (LUMO and LUMO1) of fullerene
and the highest occupied MO (HOMO and HOMO1) of
the diene, and the medium (solvation effects) also makes
a contribution to the course of the reactions of fullerenes
with various reagents. Data on phosphorylated fullerene
derivatives are virtually lacking in the literature. It should
be noted that the adducts of phosphonyl radicals to
fullerene C70 have been studied earlier by ESR spectrosꢀ
copy without their isolation in the individual form.12
When considering the reactivities of fullerenes C60 and
C70 in the reactions with carbanions of bis(dialkoxyphosꢀ
We studied the reaction of bis(diethoxyphosphoꢀ
ryl)bromomethane with fullerene C70 in toluene in the
presence of NaH as a base (Scheme 2). The reaction
proceeded at ∼20 °C to produce primarily bis(diethoxyꢀ
phosphoryl)methanofullerene C70 (3) along with sevꢀ
eral minor products (HPLC). Based on comparison of
these results with the known data13 on cycloaddition of
Nꢀmethylazomethine to fullerene C70, which gave rise to
the addition products at the a—b, c—c, and d—e bonds, it
can be concluded that the carbanion of bis(diethoxyphosꢀ
phoryl)bromomethane is added to fullerene C70 at three
types of 6,6ꢀbonds to yield product A, B, and C. Judging
from the results of calculations, the heats of formation of
methanofullerenes A and B at the a—b and c—c bonds
differ only slightly (582.89 and 583.96 kcal mol–1, respecꢀ
tively). To the contrary, the formation of cycloadduct C
at the d—e bond requires 600.6 kcal mol–1, i.e., the forꢀ
mation of the addition products to fullerene C70 at
6,6ꢀbonds of the a—b and c—c types is energetically more
preferable (calculations with the use of the GAMESS

Reactions of phosphorylbromomethanes with fullerenes Russ.Chem.Bull., Int.Ed., Vol. 51, No. 2, February, 2002
339
program package were carried out for bis(dimethoxyꢀ
phosphoryl)methanofullerene C70 as the model comꢀ
pounds).
whose chemical shifts differ also by 0.14 ppm. We asꢀ
sumed that the difference in shielding of the protons of
the ethoxy groups in bis(diethoxyphosphoryl)methanoꢀ
fullerene C70 results from the effect of the fullerene core.
Analysis of the charges on the atoms of the methoxy groups
Scheme 2
in bis(dimethoxyphosphoryl)methanofullerene[C70
]
(which was used as the model compound in quantumꢀ
chemical calculations) both at the a—b and c—c bonds
showed that the charges on these groups bound to the
same P atom are different. Apparently, this is the reason
for the difference in shielding of the protons of the ethoxy
groups bound to the P atom in compound 3. An analoꢀ
gous nonequivalence of the protons of the ethoxy groups
has been observed previously15 for 2ꢀdiethoxyphosphorylꢀ
5ꢀphenylꢀ3,4ꢀfullero[60]pyrrolidine.
To reveal the differences in the reactivity of fullerenes
C60 and C70 in cycloaddition to the carbanion of bis(diꢀ
ethoxyphosphoryl)bromomethane, we examined the reꢀ
action of the latter with a mixture of fullerenes C70—C60
(3 : 1). The course of the reaction was monitored by
HPLC, which allowed us to establish that fullerene C60
was consumed more rapidly than fullerene C70. Thus
fullerene C60 was not detected in the reaction mixture
even 40 min after the beginning of the reaction, whereas
fullerene C70 remained unconsumed after 3 h.
We succeeded in chromatographic isolation of comꢀ
pound 3 in amounts sufficient for the study by spectroꢀ
scopic methods. Based on comparison of the spectroꢀ
scopic data with the results of calculations and the data
available in the literature,13 we assigned structure A to
methanofullerene 3. This structure corresponds to the
addition at the a—b bond. Thus the 13C NMR spectrum
of compound 3 has two signals for the sp3ꢀhybridized C
atoms of the fullerene core (δ 64.10 and 65.01 with JP,C
=
5.0 Hz and JP,C = 4.7 Hz, respectively). In the case of the
c—c adduct, these C atoms would, most likely, give idenꢀ
tical signals because these atoms have the same environꢀ
ment. In addition, the signals for the sp2ꢀhybridized C
atoms involved in spinꢀspin coupling with the 31P nucleus
are also different (δ 138.13, 138.17, and 144.46, 144.50;
JP,C = 5.3 Hz in all cases).
Experimental
Fullerenes C60 (99.5% purity) and C70 (98% and 75% puriꢀ
ties) were prepared according to procedures described previꢀ
ously.16 The purities were checked by HPLC on a Gilson chroꢀ
matograph (UV detector, column with the reversed phase C18
(Partisilꢀ5 ODSꢀ3), a 1 : 1 (v/v) toluene—MeCN mixture as the
eluent). The organic solvents were dried and distilled.
The 31P NMR spectrum of the compound obtained
shows a singlet at δ 14. In the 13C NMR spectrum, 38 sigꢀ
nals belong to the C atoms of the fullerene core and the
ethoxy groups each give two signals for the C atoms. It is
known14 that the 13C NMR spectrum of unsubstituted
fullerene C70 has five signals, which differ in intensity
(1 : 2 : 1 : 2 : 1). After the attachment of the diphosphonoꢀ
methane fragment to fullerene C70, ten C atoms lying in
its equatorial region give five signals with virtually equal
intensities (δ 131.55, 131.62, 131.86, 133.95, and 134.23)
instead of one signal (δ ∼130) observed in the NMR specꢀ
trum of unsubstituted fullerene C70. It should be noted
that the 13C NMR spectrum of compound 3, like the
spectra of compounds 1 and 2, has doublet signals at
All chemical operations were carried out in an atmosphere
of dry argon. The UV spectra were recorded on a Specord Mꢀ40
spectrophotometer in CH2Cl2. The IR spectra were measured
on a Bruker Vectorꢀ22 Fourier spectrometer (in КBr pellets).
The H, 13C, and 31P NMR spectra were recorded on Bruker
1
WMꢀ250 (250 (1H) and 101.2 MHz (31P)) and Bruker MSLꢀ400
(100.57 (13C), 400.00 (1H), and 161.92 MHz (31P)) spectromꢀ
eters in CDCl3 using Me4Si and 85% H3PO4, respectively, as
the standards.
Bis(diisopropoxyphosphoryl)bromomethane. A solution of
bis(diisopropoxyphosphoryl)methane (2.9 g, 8.4 mmol) in toluꢀ
ene (10 mL) was added dropwise to a suspension of NaH (0.2 g,
8.3 mmol) in anhydrous toluene at ∼20 °C. The reaction mixture
was stirred for 1.5 h and cooled to 0—5 °C. Then a solution of
Br2 (1.35 g, 8.4 mmol) in CH2Cl2 (5 mL) was added dropwise.
The mixture was stirred for 3.5 h and washed with distilled water
(2×20 mL). The organic layer was dried with MgSO4, the solꢀ
vent was distilled off in vacuo, and the residue was distilled.
Bis(diisopropoxyphosphoryl)bromomethane was obtained in a
3
δ 138.13, 138.17 and 144.46, 144.50 with JP,C = 4.7 Hz
and 3JP,C = 5.0 Hz, respectively.
The 1H NMR spectrum of compound 3 shows signals
for the protons of the ethoxy groups bound to the P atom.
The protons of the Me groups give two triplets with equal
intensities whose chemical shifts differ by 0.14 ppm. The
signals for the protons of the methylene groups are obꢀ
served as two doublets of quartets with equal intensities
20
yield of 1.05 g (29.4%), b.p. 116 °C (0.2 Torr), nD 1.4551 (cf.
25
20
lit. data17: nD 1.4528), d4 1.2470. Found (%): C, 36.66;
H, 6.63; Br, 18.53; P, 14.49. C13H29BrO6P2. Calculated (%):
C, 36.97; H, 6.87; Br, 18.72; P, 14.69. 31P NMR, δ: 15.0.

340
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 2, February, 2002
Nuretdinov et al.
Bis(diethoxyphosphoryl)bromomethane was prepared analoꢀ
on a column with SiO2 (a 35 : 4 : 1 toluene—MeCN—hexꢀ
ane mixture as the eluent) afforded bis(diethoxyphosphoꢀ
ryl)methano[70]fullerene (3) in a yield of 39.6 mg (49.4%),
m.p. >300 °C. Found (%): P, 5.24. C79H20O6P2. Calculated (%):
P, 5.51. UV, λmax/nm (ε): 351 (14200), 365 (8900), 406 (110),
459 (320), 620 (230). IR, ν/cm–1: 456, 530, 578, 595, 643, 662,
727, 794, 904, 948, 978, 1005, 1019, 1056, 1093, 1128, 1160,
1257, 1429, 1636, 1728, 2857, 2923. 31P NMR, δ: 14.6. 1H NMR,
20
gously in 31.9% yield, b.p. 114 °C (0.15 Torr), nD 1.4660 (cf.
lit. data17: nD 1.4682), d4 1.3585. Found (%): C, 29.31;
H, 5.44; Br, 21.43; P, 16.69. C9H21BrO6P2. Calculated (%):
C, 29.51; H, 5.74; Br, 21.58; P, 16.94. 31P NMR, δ: 16.0.
Bis(diethoxyphosphoryl)methanofullerene C60 (1). A solution
of bis(diethoxyphosphoryl)bromomethane (0.220 g, 0.6 mmol)
in toluene (10 mL) was added to a solution of fullerene C60
(0.216 g, 0.3 mmol) in toluene (200 mL). The reaction mixture
was stirred for 10 min and then a suspension of NaH (0.072 g,
3 mmol) in toluene (10 mL) was added. Fullerene C60 was virtuꢀ
ally completely consumed after stirring during 1 h (HPLC). The
reaction solution was concentrated to ∼10 mL and then chromaꢀ
tographed on SiO2 (a 9 : 1 toluene—hexane mixture as the
eluent) after which the starting C60 was isolated in a yield of
0.002 g and compound 1 was obtained in a yield of 0.213 g
(71.2%) as a brown powder, m.p. >300 °C. Found (%): P, 5.81.
C69H20O6P2. Calculated (%): P, 6.16. UV, λmax/nm (ε): 326.5
25
20
3
3
δ: 1.46 (t, 6 H, JH,H = 7.3 Hz); 1.60 (t, 6 H, JH,H = 7.3 Hz);
3
3
4.39 (dq, 4 H, JH,H = 7.3 Hz, JP,H = 8.4 Hz); 4.53 (dq, 4 H,
3JH,H = 7.3 Hz, JP,H = 8.4 Hz). 13C NMR, δ: 17.28 (2 Me,
3
1JC,H = 127.3 Hz); 17.42 (2 Me, JC,H = 127.3 Hz); 25.11 (t,
1
C(61), JP,C = 154.3 Hz); 64.10 (t, Csp3, 2JP,C = 5.0 Hz); 64.82
1
1
2
(4 CH2O, JC,H = 143.6 Hz); 65.01 (t, Csp3, JP,C = 4.7 Hz);
131.55; 131.62; 131.86; 133.95; 134.23; 135.08; 138.13 (d, 2 C,
3JP,C = 5.3 Hz); 138.17 (d, 2 C, 3JP,C = 5.3 Hz); 141.73; 143.50;
143.57; 144.11; 144.46 (d, 2 C, 3JP,C = 5.3 Hz); 144.50 (d, 2 C,
3JP,C = 5.3 Hz); 144.61; 144.66; 145.22; 146.26; 146.75; 146.88;
147.35; 147.55; 147.68; 147.91; 148.41; 149.19; 149.31; 149.49;
149.81; 149.86; 150.01; 150.13; 151.38; 151.42; 151.56; 151.95;
152.06; 156.19.
(16870), 426.7 (3420), 491.3 (2193), 692.7 (110). IR, ν/cm–1
:
525, 567, 604, 978, 1019, 1096, 1157, 1200, 1256, 1428, 1527,
1635, 2894, 2926, 2977. 31P NMR, δ: 14.2. 1H NMR, δ: 1.21 (t,
3
3
12 H, 4 Me, JH,H = 7.3 Hz); 4.29 (m, 8 H, 4 CH2O, JH,H
=
=
The quantumꢀchemical calculations were carried out using
the GAMESS program package.18
7.3 Hz, JP,H = 8.7 Hz). 13C NMR, δ: 15.01 (q, 4 Me, JC,H
3
127.6 Hz); 39.38 (t, C(61), 1JP,C = 151.6 Hz); 62.15 (t, 4 CH2O,
JC,H = 148 Hz); 67.46 (t, 2 Csp3, 2JP,C = 4.6 Hz); 141.44; 142.00;
We thank N. M. Azancheev for help in analyzing the
NMR spectra of compounds 1—3.
143.29; 143.96; 144.11; 144.17; 144.20; 145.13; 145.71; 145.76;
3
145.94; 146.00; 146.08; 146.34; 146.39; 147.55 (d, 2 C, JP,C
5.0 Hz); 147.59 (d, 2 C, 3JP,C = 5.0 Hz).
=
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 99ꢀ03ꢀ
32888), by the Russian Scientific and Technical Program
"Fullerenes and Atomic Clusters" (Project No. 98008,
"Gemoꢀ2"), and by the Academy of Sciences of Tatarstan.
Bis(diisopropoxyphosphoryl)methanofullerene C60 (2) was
prepared analogously from a solution of fullerene C60 (0.216 g,
0.3 mmol), bis(diisopropoxyphosphoryl)bromomethane (0.254 g,
0.6 mmol), and NaH (0.072 g, 3 mmol) in toluene. After 15 min,
the reaction was virtually completed (HPLC). After chromaꢀ
tography on SiO2 (hexane as the eluent), unconsumed C60 was
isolated in a yield of 0.002 g and bis(diisopropoxyphosphoꢀ
ryl)methanofullerene (2) was obtained in a yield of 0.245 g
(79.2% with respect to consumed C60) as a brown powder,
m.p. >300 °C. Found (%): P, 5.56. C73H28O6P2. Calculated (%):
P, 5.89. UV, λmax/nm (ε): 326 (15300), 426.7 (3100), 491.3
(1980), 692.7 (100). IR, ν/cm–1: 526, 568, 608, 996, 1021, 1103,
1147, 1175, 1200, 1265, 1384, 1427, 1531, 1635, 2890, 2926,
2974. 31P NMR, δ: 14.3. 1H NMR, δ: 1.32 (d, 12 H, 3J =
6.0 Hz); 1.41 (d, 12 H, 3J = 6.0 Hz); 5.01 (m, 2 H); 5.07
(m, 2 H). 13C NMR, δ: 17.29 (q, 8 Me, 1JC,H = 127.1 Hz); 41.64
(t, C(61), 1JP,C = 150.1 Hz); 64.38 (dd, 4 CHO, 1JC,H = 149 Hz,
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