Synthesis, structures, and properties of new thiophosphorylated fullerenopyrrolidines. First example of the Pishchimuka reaction in fullerene derivatives

Article abstract of DOI:10.1007/s11172-006-0284-1

The reactions of fullerene C₆₀ with thiophosphorylated mono-or dialdehydes and N-methylglycine in toluene afforded new thiophosphorylated fullerenopyrrolidines, including those containing the free aldehyde group. The purity and compositions of

Full text of DOI:10.1007/s11172-006-0284-1

Russian Chemical Bulletin, International Edition, Vol. 55, No. 3, pp. 507—516, March, 2006
507
Synthesis, structures, and properties of new thiophosphorylated
fullerenopyrrolidines. First example of the Pishchimuka reaction
in fullerene derivatives
G. M. Fazleeva, V. P. Gubskaya,ꢀ F. G. Sibgatullina, V. V. Yanilkin, N. V. Nastapova, Sh. K. Latypov,
A. A. Balandina, I. E. Ismaev, V. V. Zverev, Yu. Ya. Efremov, and I. A. Nuretdinov
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.knc.ru
The reactions of fullerene C60 with thiophosphorylated monoꢀ or dialdehydes and
Nꢀmethylglycine in toluene afforded new thiophosphorylated fullerenopyrrolidines, including
those containing the free aldehyde group. The purity and compositions of the reaction products
were confirmed by MALDIꢀTOF mass spectrometry and HPLC. The structures of the reaction
products were established by twoꢀdimensional homoꢀ and heterocorrelation NMR experiꢀ
ments. The properties of the products were studied by cyclic voltammetry and quantum chemiꢀ
cal methods. The Pishchimuka rearrangement in thiophosphorylated derivatives of fullerenoꢀ
pyrrolidines was performed for the first time, and thiol esters of phosphonic acids of
fullerenopyrrolidines were prepared.
Key words: fullerene C60, thiophosphorylated fullerenopyrrolidines, NMR spectroscopy,
cyclic voltammetry, MALDIꢀTOF mass spectrometry.
Heteroorganic derivatives of fullerene have attracted
attention because they can combine the properties speꢀ
cific for both fullerene and a heteroorganic addend. Earꢀ
lier,1—8 the properties of organophosphorus derivatives of
fullerene containing the phosphoryl (P=O) group and
belonging primarily to methanofullerenes have been docuꢀ
mented. Fullerene derivatives containing the thiophosꢀ
phoryl (P=S) group have remained unknown. It is known
that the P=S group actively interacts with salts of differꢀ
ent metals9 and alkyl halides.10 This type of compounds
would be expected to be promising as biologically active
compounds and new materials for nanotechnology.
In the present study, we synthesized first representaꢀ
tives of thiophosphorylated fullerene derivatives. The charꢀ
acter of the addend attachment to the fullerene cage was
unambiguously established with the use of modern correꢀ
lation NMR techniques.
these compounds were established by spectroscopic
methods (1H and 31P NMR and IR).
The Prato reaction with the use of dialdehydes11 can
yield different products, viz., monofullerenopyrrolidines
containing the free aldehyde group, dumbbellꢀshaped bisꢀ
fullerenes, and bisꢀadducts fused onto the fullerene cage.
It appeared that heating of compounds 1—4 with
Nꢀmethylglycine and fullerene C60 in a toluene solution
(Prato reaction11) afforded the corresponding thiophosꢀ
phorylated monofullerenopyrrolidines 5—8 (Scheme 1).
Compounds 5—8 were isolated by silica gel column
chromatography. The purity of these compounds was
Results and Discussion
We prepared new thiophosphorylated dialdehydes 1
and 2 and aldehydes 3 and 4 by the reactions of the
corresponding thiophosphonic acid chlorides and
4ꢀhydroxybenzaldehyde in the presence of sodium
hydride. The reaction products were isolated in pure form
by silica gel column chromatography. The structures of
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 489—497, March, 2006.
1066ꢀ5285/06/5503ꢀ0507 © 2006 Springer Science+Business Media, Inc.

508
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
Fazleeva et al.
Scheme 1
checked by HPLC. The compositions of fullerenoꢀ
pyrrolidines 5—8 were confirmed by MALDIꢀTOF mass
spectrometry. The mass spectra contain molecular ion
peaks at m/z 1067.75 (calculated 1067.99) (5), m/z 1129.98
(calculated 1130.07) (6), m/z 1019.44 (calculated 1020.03)
(7), and m/z 1021.71 (calculated 1021.99) (8). The
UV spectra of compounds 5—8 show characteristic abꢀ
sorption bands at 258, 268, 328, and 430 nm, respectively.
The absorption band at 430 nm is indicative of the formaꢀ
tion of [6,6]ꢀclosed monoadducts.11—14 The IR spectra of
these compounds show absorption bands at 525 and
1425 cm–1 belonging to vibrations of the fullerene cage
and a number of other bands corresponding to stretching
vibrations of the attached fragments. The spectra of all
compounds contain absorption bands of P=S groups at
775—800 cm–1. The spectra of fullerenopyrrolidines 5
and 6 show absorption bands of C=O groups at 1700 and
1702 cm–1, respectively.
δ 7.81 (4 H, J = 8.1 Hz), 7.23 (2 H, J = 8.8 Hz), and 7.20
(2 H, J = 8.1 Hz). The doublet at δ 7.81 has a strongly
broadened base due, apparently, to the overlap of two
signals, one of which corresponds to the H(3´) and H(5´)
protons and the other signal corresponds to the H(3″) and
H(5″) protons (the atomic numbering scheme is given in
Scheme 1). The doublets at δ 7.20 and 7.23 were assigned
to the H(2´), H(6´) and H(2″), H(6″) protons. The signals
for the geminal protons of the C(61)H2 group of the
pyrrolidine fragment appear as an AB system at δ 4.30 and
5.00 (both d, 1 H each, J = 9.2 Hz); the H(62) proton of
this fragment resonates at δ 4.96 (s, 1 H). The signal of the
Me group at the nitrogen atom is observed at δ 2.84
(s, 3 H), and the signal of the Me group at the phosphorus
atom appears at δ 2.20 (dd, 3 H, J = 15.4 Hz, J = 1.8 Hz).
This assignment of the signals in the H NMR spectrum
was unambiguously confirmed by the results of the
2D HMBC experiment (see below).
In the 13C NMR spectrum of compound 5, the signals
for the carbon atoms bound to the hydrogen atoms were
assigned based on the analysis of the 2D HSQC experiꢀ
ment (Fig. 1). The spectrum contains the corresponding
crossꢀpeaks between the signals for the protons and the
C atoms bound to these protons due to the direct spinꢀ
spin coupling constant.
1
1
The assignment of the lines in the H and 13C NMR
spectra of compound 5 was made based on the DEPT,
2D COSY, 2D HSQC, and 2D HMBC experiments.15
The structures of individual fragments, starting from the
characteristic group (for example, from the aldehyde
group), were established by a combination of 1D and
2D experiments, which revealed homoꢀ and heteronuclear
correlations.
The 1H NMR spectrum of compound 5 shows signals
for the aldehyde proton (δ 9.94), aromatic protons, and
protons of the pyrrolidine fragment and the Me groups.
The signals for the aromatic protons appear as doublets at
The 2D HMBC spectrum of compound 5 (Fig. 2)
shows a correlation between the signals for the aldehyde
protons and the C atoms at δ 130.84 and 122.05. Taking
into account that the spinꢀspin coupling constant 3J is
larger than 2,4J, the higher intensity of the crossꢀpeak is

Thiophosphorylated fullerenopyrrolidines
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
509
Hꢀ3´,5´; Hꢀ3″,5″
CH3N
Hꢀ62
CH3P
Hꢀ2″,6″
Hꢀ2´,6´
COH
Hꢀ61
Hꢀ61
δ
CH3P/CH3P
20
CH3P
CH3N
40
CH3N/CH3N
Hꢀ61/Cꢀ61
60
Cꢀ61
Cꢀ62
80
Hꢀ62/Cꢀ62
100
120
140
160
180
Cꢀ2´,6´
Cꢀ2″,6″
Cꢀ3´,5´
Cꢀ3″,5″
Hꢀ2´,6´/Cꢀ2´,6´
Hꢀ2″,6″/Cꢀ2″,6″
Hꢀ2´,5´/Cꢀ3´,5´
Hꢀ3″,5″/Cꢀ3″,5″
COH
9
COH
8
7
6
5
4
3
2
1
δ
Fig. 1. 2D HSQC spectrum (1H—13C) of compound 5.
Hꢀ62
Hꢀ61
Hꢀ2″,6″
COH
CH3P
Hꢀ61
CH3N
Hꢀ3´,5´; Hꢀ3″,5″
Hꢀ2´,6´
δ
20
CH3P
CH3N
Hꢀ62/NCH3
Hꢀ61/NCH3
40
NCH3/Hꢀ61
NCH3/Hꢀ62
Hꢀ61/Cꢀ1
Hꢀ61/Cꢀ1
60
Cꢀ61
Cꢀ62
Hꢀ62/Cꢀ61
Hꢀ61/Cꢀ6
80
Hꢀ61/Cꢀ62
Hꢀ62/Cꢀ6
100
120
140
160
180
Cꢀ2´,6´
Cꢀ2″,6″
Cꢀ3´,5´
Hꢀ2″,6″/Cꢀ4″
COH/Cꢀ2″,6″
COH/Cꢀ3″,5″
Hꢀ62/Cꢀ3´,5´
Hꢀ62/Cꢀ4´
Cꢀ3″,5″
Hꢀ62/Cꢀ5, Cꢀ7
CH3P/Cꢀ1´
Hꢀ2´,6´/Cꢀ4´
COH/Cꢀ4″
Hꢀ2´,6´/Cꢀ1´
Hꢀ2″,6″/Cꢀ1″
Hꢀ3″,5″/Cꢀ1″
CH3P/Cꢀ1″
Hꢀ61/Cꢀ2, Cꢀ10
Hꢀ61/Cꢀ2, Cꢀ10
Hꢀ2″,6″/COH
Hꢀ3″,5″/COH
COH
9
8
7
6
5
4
3
δ
Fig. 2. 2D HMBC spectrum (1H—13C) of compound 5.
evidence that this peak corresponds to the correlation of
this proton with the C(3″) and C(5″) atoms (δ 130.84).
The second (less intense) crossꢀpeak corresponds to the
correlation of the aldehyde proton with the C(2″) and
C(6″) atoms. Therefore, the C(3″), C(5″), C(2″), and
C(6″) atoms were unambiguously identified. The assignꢀ
ment of the corresponding protons, viz., H(3″), H(5″)
(δ 7.81) and H(2″), H(6″) (δ 7.23), was confirmed using

510
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
Fazleeva et al.
the 2D HSQC experiment. In addition, the 2D HMBC
spectrum (see Fig. 2) contains crossꢀpeaks between the
H(2″), H(6″)/H(3″), and H(5″) protons and the C atom
and the C(1) atom (δ 68.57) and between the H(61)
(δ 5.00) and H(62) protons (δ 4.96) and the C(6) atom
(δ 76.73). In addition, there are crossꢀpeaks between the
H(61) protons (δ 5.00 and 4.30) and the C(2) and C(10)
atoms (δ 155.67 and 153.41, respectively) and between
the H(62) proton (δ 4.96) and the C(5) and C(7) atoms
(δ 152.68 and 152.48, respectively). Therefore, we identiꢀ
fied the C atoms of the fullerene cage adjacent to the
attachment site of the addend. The chemical shifts of the
C(1) and C(6) atoms (their nonaromaticity) confirm the
closed character of the attachment of the addend.
It should be noted that a broadening of the signals
observed for the H(3´) and H(5´) protons and, to a lesser
extent, for the H(2´) and H(6´) protons is, evidently,
attributed to relatively slow (on the NMR time scale)
rotation about the C(62)—C(4´) bond. Apparently, this is
associated with the steric factors due to the closely spaced
fullerene cage. Analogously, the signals for the C(2´),
C(6´) and C(3´), C(5´) atoms of this fragment are also
broadened compared to other resonances.
The structure of 6 differs from that of 5 by the subꢀ
stituent at the thiophosphoryl group (the Ph fragment
instead of the Me group). The 1H NMR spectrum of
compound 5 is similar to that of 6. The only difference is
that the aromatic region shows additional signals belongꢀ
ing to the protons of the phenyl group at the phosphorus
atom, whereas the signal for the protons of the PMe group
disappears. The structure of compound 6 was established
as described above. The chemical shifts in the 1H and
13C NMR spectra are given in the Experimental section.
The 13C NMR spectrum of compound 6 shows resoꢀ
nances for the corresponding carbon atoms of the phenyl
fragment at the phosphorus atom. The assignment of the
signals for the C atoms of this fragment bound to the
H atoms was made based on the analysis of the 2D HSQC
spectrum. Then all other signals were unambiguously asꢀ
signed based on the 2D HMBC spectrum.
The character of the attachment of the addend to the
fullerene core was also established based on the HMBC
correlations. The 2D HMBC spectrum shows the correꢀ
sponding crossꢀpeaks between the H(61) protons of the
pyrrolidine ring and the C(1) atom at δ 68.96 and between
the H(61) and H(62) protons and the C(6) atom at δ 77.12.
In addition, the 2D HMBC spectrum shows crossꢀpeaks
between the protons of the pyrrolidine fragment and the
C(2)/C(10) and C(5)/C(7) atoms of fullerene. Therefore,
the closed type of the attachment of the addend is obꢀ
served both in compounds 6 and 5.
2
at δ 154.57 (d, C(1″), JC,P = 9.7 Hz). There is also a
correlation between the protons at δ 7.23 (H(2″) and
H(6″)) and the C atom at δ 133.45 (C(4″)). This made it
possible to establish the structure of the fragment from the
aldehyde group up to the second oxygen atom.
The resonances for the carbon atoms of the pyrrolidine
ring were determined from the analysis of the 2D HSQC
spectrum (see Fig. 1; δ 69.73 (C(61)) and 82.50 (C(62)).
The crossꢀpeak in the 2D HMBC spectrum between the
signal for the pyrrolidine proton at δ 4.96 (H(62)) and the
signal for the carbon atom of one of the benzene fragꢀ
ments at δ 130.16 (see Fig. 2) provides evidence that this
signal corresponds to the C(3´) and C(5´) atoms. The
assignment of the H(3´) and H(5´) protons (δ 7.81) was
confirmed based on the results of the 2D HSQC experiꢀ
ment (see Fig. 1). The resonance for the H(2´) and H(6´)
protons (δ 7.20) was identified from the 2D COSY specꢀ
trum. Analogously, the C(2´) and C(6´) atoms (δ 121.66)
were determined from the HSQC spectrum (see Fig. 1)
after the identification of the H(2´) and H(6´) protons.
The 2D HMBC spectrum (see Fig. 2) shows crossꢀpeaks
between the H(2´), H(6´), and H(62) protons and the
carbon atom at δ 134.09 (C(4´)) and between the H(2´)
and H(6´) protons and the carbon atom at δ 150.00 (d,
2
C(1´), JC,P = 9.7 Hz). Therefore, the structure of the
second benzene fragment was confirmed, and the bond
between this fragment and the pyrrolidine ring was estabꢀ
lished.
In addition, we revealed the correlation between the
protons and the carbon atoms of the pyrrolidine ring. The
2D HMBC spectrum (see Fig. 2) shows the H(61)/C(62)
and H(62)/C(61) correlations and has crossꢀpeaks beꢀ
tween the H(61) and H(62) protons and the carbon atom
of the NMe group at δ 39.71. The protons at δ 2.84 (MeN)
interact with the carbon atoms at δ 69.73 (C(61)) and
82.50 (C(62)).
The bonds between the fragments located on the opꢀ
posite sides of the phosphorus atom were determined based
on the characteristic throughꢀtwoꢀbond spinꢀspin couꢀ
pling constant for the quaternary C(1´) and C(1″) atoms
(2JC,P = 9.7 Hz).16 Moreover, the 2D HMBC experiment
independently confirmed the presence of the bond beꢀ
tween the fragments based on the crossꢀpeaks between
the PMe protons (δ 2.20) and the C(1´) and C(1″) atoms
(see Fig. 2).
The 2D HMBC experiments allowed us, first, to unꢀ
ambiguously reveal the bond between the pyrrolidine fragꢀ
ment and the fullerene cage and, second, to determine
the chemical shifts of the sp3ꢀhybridized C atoms, to which
the pyrrolidine fragment is attached, and thus establish
the character of this bond. The 2D HMBC spectrum shows
a correlation between the H(61) protons (δ 5.00 and 4.30)
The structures of compounds 7 and 8 were analoꢀ
gously confirmed by NMR spectroscopic data.
The chemistry of functionalized fullerene derivatives
is poorly studied. However, it is known that, in the presꢀ
ence of alkyl halides, thionophosphates are prone to the
thioneꢀthiol rearrangement discovered by Pishchimuka.10
Earlier,12 it has been demonstrated that the reaction of

Thiophosphorylated fullerenopyrrolidines
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
511
Scheme 2
fullerenopyrrolidines with MeI produces their cationic
derivatives, which are higher soluble in polar solvents
compared to the starting compounds. Based on these data,
we studied the reaction of thiophosphorylated fullerenoꢀ
pyrrolidine 7 with iodomethane. Actually, this reaction
with excess MeI leads to quaternization of the nitrogen
atom of the pyrrolidine fragment with the simultaꢀ
neous rearrangement of the phosphorusꢀcontaining group
(Scheme 2). The yield of the final product was 76%.
Therefore, we synthesized the first onium thioloꢀ
phosphoryl derivative of fullerenopyrrolidine 9 by the
Pishchimuka thioneꢀthiol rearrangement. This compound
is readily soluble in polar solvents, for example, in DMSO.
The structure of compound 9 was confirmed by spectroꢀ
scopic methods. For example, the mass spectrum of comꢀ
pound 9 has the fragment peak [M+ – MeI] at m/z 900. In
the IR spectrum of compound 9, the lowꢀintensity abꢀ
sorption band of the P=Sꢀgroup (782 cm–1) is absent, and
the more intense band of the P=O group (1174 cm–1) is
observed. The 31P NMR spectrum of compound 9 shows
a signal with the chemical shift characteristic of the
thiolophosphoryl fragment (δP 60.80; cf. δP 100.00 for the
starting compound 7).
The structure of product 9 was confirmed also by 1D
and 2D NMR experiments. The signals for the protons of
the pyrrolidine fragment (H(62), δ 7.27; H(61), δ 6.03
and 5.79; Me2N+, δ 4.23 and 3.68) are observed at lower
field compared to the corresponding protons in comꢀ
pounds 5—8 due to the presence of the positive charge on
the nitrogen atom. The structure of the pyrrolidine fragꢀ
ment as well as the fact and the character of its attachꢀ
ment to the fullerene cage were unambiguously estabꢀ
lished based on the 2D HMBC spectrum.
With the aim of examining the possibility of the use of
compounds 5—8, we studied their electrochemical propꢀ
erties. In particular, electrochemical reduction on a glassyꢀ
carbon electrode in an oꢀdichlorobenzene (DCB)—DMF
(3 : 1, v/v)/0.1 M Bu4NBF4 system was studied by cyclic
voltammetry.
Electrochemical reduction of fullerenopyrrolidines 7
and 8 proceeds analogously to reduction of the represenꢀ
tatives of this class of [60]fullerene derivatives studied
earlier.13,14 The cyclic voltammograms show three reducꢀ
tion peaks as well as three conjugated oxidation peaks on
the reverse scan (Table 1, Fig. 3). The heights of the
reduction peaks correspond to the oneꢀelectron level. The
Table 1. Cyclic voltammetric data (reduction peak potentials (Ep,red) and oxidation peak potentials
(Ep,ox)) for electrochemical reduction of C60 and fullerenopyrrolidines 5—8 in an DCB—DMF
(3 : 1, v/v)/0.1 M Bu4NBF4 solution system on a glassyꢀcarbon electrode*
Comꢀ
pound
–Е1р,red
–Е1р,ox
–Е2р,red
–Е2р,ox
–Е3р,red
–Е3р,ox
–Е4р,red
–Е4р,ox
V
С60
5
6
7
8
0.96
1.08
1.06
1.09
1.09
0.90
1.02
1.00
1.02
1.02
1.40
1.51
1.49
1.53
1.53
1.33
1.45
1.43
1.46
1.46
1.90
2.10
2.09
2.10
2.10
1.84
2.02
2.00
2.04
2.03
2.39
2.33
2.32
—
2.32
2.27
2.26
—
—
—
* The potentials were measured relative to the standard potential of the Fc+/Fc redox system with the
use of Ag/0.01 M AgNO3 solution in MeCN as the reference electrode at a potential scan rate
of 20 mV s–1
.

512
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Fazleeva et al.
the latter compounds are lower than those of compounds
7 and 8 at the reverse potential sweep from the third
reduction peak. Yet another characteristic feature of the
third reduction peak is that it is higher than the oneꢀ
electron level. The ratio of the height of the third peak to
the height of the first peak (H ) increases with decreasing
potential scan rate, which is indicative of the kinetic naꢀ
ture of the peak current.
i/µA
1
0
5
6
–1
i/µA
1
0
Comꢀ
pound
H at a potential scan rate/mV s–1
–1
20
50
100
5
6
1.3
1.7
1.1
1.2
1.0
1.1
i/µA
1
0
–1
Evidently, slow chemical reactions proceed in the radiꢀ
cal trianions to give species electrochemically active in
this potential region. The radical trianion of fullerenoꢀ
pyrrolidine 7, which contains an analogous thiophosꢀ
phonate group but in which the benzaldehyde group is
absent, is stable. Consequently, the possibility of subseꢀ
quent chemical reactions in the radical trianions of comꢀ
pounds 5 and 6 is associated with the simultaneous presꢀ
ence of the thiophosphonate and benzaldehyde fragments.
The absence of the fourth peak for compounds 7 and 8
and its presence for fullerenopyrrolidines 5 and 6 is unꢀ
ambiguous evidence that this reduction peak is associated
with the electron transfer to the benzaldehyde fragment.
The thiophosphonate fragment possesses the electronꢀ
withdrawing properties, thus facilitating the electron
transfer.
It is known18 that aryl phosphates are electrochemiꢀ
cally efficiently reduced not only at an electrode but also
homogeneously by organic electron carriers. This process
is accompanied by the twoꢀelectron irreversible C—O
bond cleavage to form the phosphate ion and arenes.
Analogously, it can be assumed that electrochemical reꢀ
duction of compounds 5 and 6 is accompanied by the
slow intramolecular electron transfer from the radical
trianion of the fullerene cage to the thiophosphonate fragꢀ
ment facilitated by the presence of the electronꢀwithꢀ
drawing benzaldehyde group. This process is responsible
for an increase in the hight of the third reduction peak
relative to the oneꢀelectron level and consumption of the
radical trianions.
7
8
i/µA
1
0
–1
–1
–2
E/V
Fig. 3. Cyclic voltammograms of fullerenopyrrolidines 5—8
recorded on a glassyꢀcarbon electrode in an DCB—DMF
(3 : 1, v/v)/Bu4NBF4 system (C = 0.1 mol L–1) at a potential
scan rate of 20 mV s–1, T = 295 K, and C = 1•10–3 mol L–1
.
difference between the reduction peak potentials and the
corresponding oxidation peaks is equal to the theoretical
value for the reversible oneꢀelectron transfer17
∆Ep = Ep,oxm – Ep,red ≈ 60 mV,
m
m = 1—3.
Consequently, fullerenopyrrolidines 7 and 8 reversꢀ
ibly and stepwise accept three electrons per molecule to
form finally the radical trianions in the accessible potenꢀ
tial region (Scheme 3).
Scheme 3
A + e
A•– + e
A2– + e
A3•–
Consequently, the stepwise threeꢀelectron transfer to
the fullerene cage gives rise to stable radical anions,
dianions, and unstable radical trianions. The radical
trianions of bisꢀfullerenopyrrolidines, in which the thioꢀ
phosphonate group is absent, are quite stable.
Therefore, the presence of the thiophosphonate and
thiophosphate groups in the molecule has no effect on
electrochemical reduction of fullerenopyrrolidines 7 and 8.
The presence of the thiophosphonate and/or benzaldeꢀ
hyde groups in compounds 5 and 6 is responsible for the
specific features of their behavior in particular reduction
The cyclic voltammograms of compounds 5 and 6
have four reduction peaks. The first two reduction steps
are identical to reduction of fullerenopyrrolidines 7 and 8.
The stepwise reversible twoꢀelectron transfer to the
fullerene cage giving rise to stable radical anions and
dianions was observed. The potential of the third step also
corresponds to the third electron transfer to the fullerene
cage of fullerenopyrrolidines. However, unlike fullerenoꢀ
pyrrolidines 7 and 8, the radical trianions of compounds 5
and 6 are unstable. Hence, the anodic oxidation peaks of

Thiophosphorylated fullerenopyrrolidines
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
513
Conforꢀ
mer
E
/au
∆E
µ/D
τ
dP=S
/Å
steps. At the same time, the transfer of the first three
electrons to the fullerene cage occurs in all cases, and the
properties typical of monofullerenopyrrolidines are obꢀ
served in these steps.
/kcal mol–1
/deg
A
B
–3774.88773
–3774.88377
0.00
2.48
5.92
3.89
–47 1.951
165 1.944
It is more difficult to reduce fullerenopyrrolidines 5—8
than [60]fullerene. The first peak of monoadducts 5—8 is
shifted to more cathodic potentials by 100—130 mV. The
differences between the potentials of the second electron
transfer are approximately equal to the above values. The
difference in the potentials of the third reduction peaks is
more substantial. These results mean that the distortion of
the overall conjugation πꢀsystem of fullerene C60 by inꢀ
troducing the pyrrolidine ring decreases the electron afꢀ
finity of the compound.
We studied the structure of fullerenopyrrolidine 7 by
density functional theory with the use of the nonempirical
exchangeꢀcorrelation potential19 and the tripleꢀzeta basis
set DFT/PBE/TZ2P using the PRIRODA program packꢀ
age.20 According to the calculations, the pyrrolidine ring
adopts an Nꢀenvelope conformation. The methyl group
deviates toward the C—H bond of the pyrrolidine ring.
The plane of the benzene ring is perpendicular to that of
the pyrrolidine ring. Depending on the C—O—P=S torꢀ
sion angle, which characterizes internal rotation of the
thiophosphoryl group relative to the plane of the benzene
ring about the P—O bond, the molecule adopts two stable
conformations referred to as A and B (Fig. 4). The major
structure A is characterized by the deviation of the P=S
bond toward the fullerene cage. The total (E) and relative
(∆E) energies, the dipole moments (µ), the C—O—P=S
torsion angles (τ), and the P=S bond lengths (dP=S) for
the conformers A and B of compound 7 calculated by the
DFT/PBE/TZ2P method are given below.
The preferable structure A is more polar compared
to the conformer B. The dipole moment calculated
for the conformation A is equal to the experimental
value (5.3 D).21
Experimental
Analysis by HPLC was carried out on a Gilson chromatoꢀ
graph equipped with an UV detector (C18 reversedꢀphase colꢀ
umn (Partisilꢀ5 ODSꢀ3); toluene—MeCN, 1 : 1, v/v, as the
eluent). The organic solvents were dried and distilled before use.
Fullerene C60 of 99.9% purity (produced by the G. A. Razuvaev
Institute of Organometallic Chemistry of the Russian Academy
of Sciences, Nizhny Novgorod) was used. The starting
thiophosphorylated aldehydes and dialdehydes 1—4 were preꢀ
pared according to known procedures.22,23 All chemical operaꢀ
tions were carried out under dry argon.
The UV spectra were recorded on a Specord Mꢀ40 spectroꢀ
photometer in CH2Cl2. The IR spectra were measured on a
Bruker Vector 22 Fourierꢀtransform spectrometer (KBr pellets).
The 1H, 13C, and 31P NMR spectra were recorded on Bruker
MSLꢀ400 (400.00 MHz for 1H, 162.0 MHz for 31P, and
1
100.6 MHz for 13C) and Bruker Avanceꢀ600 (600 MHz for H)
spectrometers at 30 °C. The 1D DEPT, 2D COSY, 2D HSQC,
and 2D HMBC experiments were performed on a Bruker
Avanceꢀ600 spectrometer. The chemical shifts were measured
relative to the signals for the residual protons of the deuterated
solvent or the carbon nuclei of CDCl3 (1H and 13C, respecꢀ
tively) or relative to 85% H3PO4 (31P) as the external standard.
The mass spectra were obtained on a MALDIꢀTOF MS inꢀ
S
P
O
O
C
H
N
A
B
Fig. 4. Stereo view of the conformations A and B of compound 7 according to calculations by the DFT/PBE/TZ2P method.

514
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
Fazleeva et al.
strument (DynamoThermoꢀBioANALYSIS) using trihydroxyꢀ
anthracene as the matrix.
7.81 and 7.86 (both d, 2 H, H arom., J = 8.5 Hz); 9.91 (s,
1 H, C(O)H).
Cyclic voltammograms were recorded on a PIꢀ50ꢀ1 poꢀ
tentiostat equipped with an H307/2 XꢀY recorder. A glassyꢀ
carbon disk electrode (d = 2 mm) pressed into glass served as a
working electrode. A platinum wire was used as an auxiliary
electrode. Before each measurement, the electrodes were subꢀ
jected to mechanical polishing. The potentials were measured
relative to the standard potential of the ferrocene—ferrocenium
ion redox system (Fc/Fc+) using an Ag/AgNO3 silver reference
electrode (0.01 mol L–1) in MeCN. Dissolved oxygen was reꢀ
moved by bubbling nitrogen through the solution at 295 K.
Quantum chemical calculations were carried out using the
PRIRODA program19,20 (DFT).
O,OꢀDiethyl Oꢀ(4ꢀformylphenyl) thiophosphate (4). Under
the conditions described above for the synthesis of comꢀ
pounds 1—3, compound 4 was synthesized as a viscous yellow
oil in a yield of 2.8 g (41%) from NaH (0.5 g, 0.0208 mol),
4ꢀhydroxybenzaldehyde (2.1 g, 0.017 mol), and O,Oꢀdiethylꢀ
thionophosphonic acid chloride (3 g, 0.016 mol). Found (%):
C, 47.95; H, 5.32; P, 10.06; S, 11.54. C11H15O4PS. Calcuꢀ
lated (%): C, 48.18; H, 5.51; P, 11.29; S, 11.68. IR, ν/cm–1
:
647, 740, 822, 926, 1023, 1099, 1160, 1220, 1504, 1599, 1704,
2986. 31P NMR (CDCl3), δ: 58. 1H NMR (CDCl3), δ: 1.32
(t, 6 H); 4.17 and 4.23 (both m, 4 H); 7.26 and 7.81 (both dd,
4 H, H arom.); 9.93 (s, 1 H, C(O)H).
BisꢀO,Oꢀ(4ꢀformylphenyl) methylthiophosphonate (1). A soꢀ
lution of 4ꢀhydroxybenzaldehyde (4 g, 0.0164 mol) in THF was
added dropwise to a suspension of NaH (1.0 g, 0.042 mol) in
THF at 10 °C. The reaction mixture was stirred at ~20 °C for
40 min. Then a solution of methylthiophosphonic acid dichloꢀ
ride (2.4 g, 0.0161 mol) in THF was added dropwise. The reacꢀ
tion mixture was stirred for 12 h and extracted with CHCl3. The
organic layer was dried with MgSO4 and concentrated in vacuo.
The residue was purified by silica gel column chromatography
(AcOEt—hexane, 1 : 3, as the eluent). Compound 1 was obꢀ
tained in a yield of 3.1 g (60%) as white crystals, m.p. 89—90 °C.
Found (%): C, 56.30; H, 4.10; P, 9.63; S, 10.02. C15H13O4PS.
1ꢀ{4ꢀ[Oꢀ(4ꢀFormylphenyl)methylthiophosphonoxy]phenyl}ꢀ
Nꢀmethyl[60]fullereno[1,2ꢀc]pyrrolidine (5). A solution of
fullerene C60 (0.216 g, 0.3 mmol), Nꢀmethylglycine (0.080 g,
0.9 mmol), and compound 1 (0.144 g, 0.45 mmol) was refluxed
in toluene (200 mL) under argon for 15 h. The reaction mixture
was washed with water (2×30 mL) and concentrated in vacuo.
The product was isolated by silica gel column chromatography
(hexane—toluene, 1 : 1, as the eluent). Compound 5 was obꢀ
tained in a yield of 0.0733 g (34% based on consumed C60). UV,
λ
max/nm (ε): 258 (45000), 326 (13000), 431.2 (1800), 696 (280).
IR, ν/cm–1: 524, 573, 598, 643, 748, 796, 832, 905, 1014, 1099,
1122, 1155, 1189, 1295, 1329, 1422, 1460, 1498, 1593, 1656,
1700, 2777, 2853, 2924, 3429. 31P NMR (CS2—CDCl3), δ: 89.96.
1H NMR (CS2/CDCl3), δ: 2.20 (dd, 3 H, P(S)Me, J = 15.4 Hz,
J = 1.8 Hz); 2.84 (s, 3 H, NMe); 4.96 (s, 1 H, CH of pyrrolidine);
4.30, 5.00 (both d, 2 H, CH2 of pyrrolidine, J = 9.2 Hz); 7.20
and 7.23 (both d, 4 H, H arom., J = 8.8 Hz); 7.81 (d, 4 H,
H arom., J = 8.1 Hz); 9.94 (s, 1 H, C(O)H). 13C NMR
(CS2—CDCl3), δ: 22.00 (P(S)Me); 39.71 (s, NMe); 68.57
(C(1)); 69.73 (C(61)); 76.75 (C(6)); 82.50 (C(62)); 121.66 (C(2´,
C(6´)); 122.05 (C(2″), C(6″)); 130.16 (C(3´), C(5´)); 130.84
(C(3″), C(5″)); 133.45 (C(4″)); 134.09 (C(4´)); 135.41; 135.68;
136.21; 136.67; 139.19; 139.72; 139.99; 141.30; 141.43; 141.53;
141.60; 141.69; 141.78; 141.89; 141.96; 142.35; 142.77; 142.91;
144.30; 144.44; 145.05; 145.34; 145.42; 145.86; 146.04; 146.19;
147.02; 150.00 (d, C(1´), 2JC,P = 9.7 Hz); 152.48 (C(7)); 152.68
Calculated (%): C, 56.25; H, 4.09; P, 9.65; S, 10.01. IR, ν/cm–1
:
622, 649, 706, 729, 799, 830, 904, 1010, 1103, 1157, 1211,
1304, 1391, 1422, 1501, 1597, 1700, 2922. 31P NMR (CDCl3),
δ: 92.16. 1H NMR (CDCl3), δ: 2.25 (d, 3 H, J = 15.9 Hz); 7.27
and 7.29 (both dd, 4 H, H arom., J = 2.5 Hz, J = 8.5 Hz);
7.87 and 7.99 (both d, 4 H, H arom., J = 8.5 Hz); 9.96 (s,
2 H, C(O)H)).
BisꢀO,Oꢀ(4ꢀformylphenyl) phenylthiophosphonate (2). Comꢀ
pound 2 was synthesized analogously as white crystals, m.p.
93—95 °C, in a yield of 4.5 g (83%) from NaH (0.9 g, 0.01 mol),
4ꢀhydroxybenzaldehyde (4.2 g, 0.0098 mol), and phenylthioꢀ
phosphonic acid dichloride (3.0 g, 0.008 mol) followed by puriꢀ
fication by silica gel column chromatography (AcOEt—hexane,
1 : 3, as the eluent). Found (%): C, 62.96; H, 3.81; P, 8.03;
S, 8.21. C20H15O4PS. Calculated (%): C, 62.83; H, 3.95; P, 8.10;
S, 8.39. IR, ν/cm–1: 606, 655, 693, 711, 730, 753, 768, 836, 850,
910, 950, 970, 1014, 1123, 1156, 1190, 1207, 1222, 1296, 1393,
1423, 1438, 1501, 1588, 1706, 2362, 2823. 31P NMR (CDCl3),
δ: 82.60. 1H NMR (CDCl3), δ: 7.27 and 7.29 (both dd, 4 H,
H arom., J = 1.3 Hz, J = 8.5 Hz); 7.87 and 7.99 (both d, 4 H,
H arom., J = 8.5 Hz); 7.59 and 8.10 (both m, H arom.); 9.93 (s,
2 H, C(O)H).
Oꢀ(4ꢀFormylphenyl) Oꢀpropyl ethylthiophosphonate (3). Comꢀ
pound 3 was synthesized as a viscous yellow oil in a yield of 1.9 g
(87%) according to the aboveꢀdescribed procedure from NaH
(0.25 g, 0.01 mol), 4ꢀhydroxybenzaldehyde (1.2 g, 0.0098 mol),
and Oꢀpropylethylthiophosphonic acid chloride (1.5 g,
0.008 mol) followed by purification by silica gel column
chromatography. Found (%): C, 52.61; H, 6.02; P, 11.03; S,
11.52. C12H17O3PS. Calculated (%): C, 52.93; H, 6.29; P, 11.37;
S, 11.78. IR, ν/cm–1: 643, 742, 822, 936, 1020, 1099, 1123,
1222, 1502, 1704, 2925. 31P NMR (CDCl3), δ: 100.30. 1H NMR
(CDCl3), δ: 0.92 (t, 3 H, Prn); 1.22 (t, 3 H, Me); 1.31 (t, 2 H,
CH2); 2.18 (m, 2 H, CH2); 3.98 and 4.13 (both m, 2 H, Prn);
7.13 and 7.29 (both dd, 2 H, H arom., J = 9.6 Hz, J = 17.9 Hz);
2
(C(5)); 153.41 (C(10)); 154.57 (d, C(1″), JC,P = 9.7 Hz);
188.86 (C(O)H). MALDIꢀTOF MS, found: m/z 1067.75 [M]+.
C77H18NO3PS. Calculated: M = 1067.99.
1ꢀ{4ꢀ[Oꢀ(4ꢀFormylphenyl)phenylthiophosphonoxy]phenyl}ꢀ
Nꢀmethyl[60]fullereno[1,2ꢀc]pyrrolidine (6). Under the condiꢀ
tions described above for the synthesis of fullerenopyrrolidine 5,
compound 6 was prepared from fullerene C60 (0.216 g,
0.3 mmol), compound 2 (0.1375 g, 0.36 mmol), and Nꢀmethylꢀ
glycine (0.080 g, 0.9 mmol) in toluene (200 mL) in a yield of
0.035 g (14% based on consumed C60). UV, λmax/nm (ε): 255.8
(46200), 326 (11000), 429.8 (2100), 697 (310). IR, ν/cm–1: 525.5,
725, 906, 1121, 1156, 1186, 1216, 1282, 1502, 1597, 1702.
31P NMR (CDCl3), δ: 83.44. 1H NMR (CDCl3), δ: 2.80 (s, 3 H,
NMe); 4.93 (s, 1 H, CH of pyrrolidine); 4.26 and 4.98 (both d,
2 H, CH2 of pyrrolidine, J = 9.2 Hz); 7.15 and 7.27 (both d, 4 H,
H arom., J = 8.8 Hz); 7.52—8.08 (m, 5 H, Ph); 7.83 (d, 4 H,
H arom.); 9.98 (s, 1 H, C(O)H). 13C NMR (CDCl3), δ: 39.98 (s,
NMe); 68.96 (C(1)); 69.96 (C(61)); 77.12 (C(6)); 82.75 (C(62));
122.30 (C(2´), C(6´)); 125.27 (C(2″), C(6″)); 128.19 (C(3´),
2
C(5´)); 128.62 (C(3′″), C(5′″), JC,P = 15.8 Hz); 129.00 (C(3″),
C(5″)); 131.55 (C(2′″), C(6′″), 2JC,P = 12.2 Hz); 132.41 (C(1′″));

Thiophosphorylated fullerenopyrrolidines
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
515
133.26 (C(4′″), 2JC,P = 3.1 Hz); 133.50 (C(4″)); 134.46 (C(4´));
136.20; 137.10; 138.60; 139.00; 139.20; 139.50; 140.00;
140.90; 141.10; 141.30; 141.40; 141.50; 141.60; 141.70; 141.90;
142.00; 142.30; 142.60; 143.30; 143.50; 143.60; 143.80; 144.00;
144.50; 144.60; 144.70; 144.80; 145.10; 145.22; 145.44; 145.60;
145.70; 145.80; 146.00; 146.50; 149.59; 150.36 (d, C(1´),
2JC,P = 9.7); 153.06 (C(7)); 153.09 (C(5)); 153.83 (C(10));
1ꢀ[4ꢀ(PꢀEthylꢀPꢀmethylthiophosphonoxy)phenyl]ꢀN,Nꢀdiꢀ
methyl[60]fullereno[1,2ꢀc]pyrrolidinium iodide (9). A mixture of
fullerenopyrrolidine 7 (0.030 g, 0.00003 mol) and MeI (0.3 mL,
0.005 mol) was heated in a sealed tube to 70—80 °C for 28 h.
Then the precipitate was filtered off and washed with toluene.
Compound 9 was obtained in a yield of 0.025 g (76%). IR,
ν/cm–1: 526, 747, 849, 909, 972, 1174 (P=O), 1216, 1427, 1459,
1507, 2924, 3444. 31P NMR (DMSOꢀd6), δ: 60.85. 1H NMR
(DMSOꢀd6), δ: 1.22 (3 H, CH3 (Et)); 2.27 (2 H, CH2 (Et));
2.29 (3 H, PSMe); 3.83 and 4.22 (6 H, NMe2); 7.27 (s, 1 H, CH
of pyrrolidine); 5.78 and 6.04 (both s, 2 H, CH2 of pyrrolidine);
7.52 (d, 2 H, H arom.); 8.11 (br.s, 2 H, H arom.). 13C NMR
(DMSOꢀd6), δ: 5.80; 11.27; 18.20; 46.42, 52.35 (NMe2); 67.11
(C(1)); 72.64 (C(6)); 73.26, 83.33, 121.38, 122.33, 134.94, 146.25
(C arom.); 137.05; 139.15; 139.57; 140.55; 140.68; 140.95;
141.05; 141.36; 141.53; 141.97; 142.06; 142.17; 142.39; 143.65;
143.91; 144.42; 144.47; 144.64; 144.77; 144.88; 144.95; 145.04;
145.35; 145.49; 145.65; 146.02; 148.85; 150.46; 150.96; 152.98.
2
155.22 (d, C(1″), JC,P = 9.7 Hz); 156.16 (C(2)); 190.10
(C(O)H). MALDIꢀTOF MS, found: m/z 1129.98 [M]+.
C
82H20NO3PS. Calculated: M = 1130.07.
NꢀMethylꢀ1ꢀ{4ꢀ[(Oꢀpropyl)ethylthiophosphonoxy]pheꢀ
nyl}[60]fullereno[1,2ꢀc]pyrrolidine (7). A solution of fullerene
C60 (0.216 g, 0.3 mmol), compound 3 (0.167 g, 0.6 mmol), and
Nꢀmethylglycine (0.080 g, 0.9 mmol) in toluene (200 mL) was
refluxed under argon for 17 h. The reaction mixture was washed
with water (2×30 mL) and concentrated in vacuo. The prodꢀ
uct was isolated by silica gel column chromatography (hexꢀ
ane—toluene—MeCN, 1 : 2 : 0.5, as the eluent). Compound 7
was obtained in a yield of 0.101 g (40% based on consumed C60).
UV, λmax/nm (ε): 256 (45800), 326 (12000), 431.6 (1900),
MALDIꢀTOF MS, found: m/z 720.00 (C60), 990.73 ([M]+
–
MeI). C73H21INO2PS. Calculated: M = 1132.74.
696 (290). IR, ν/cm–1
: 525, 753, 782, 842, 906, 989,
1215, 1502. 31P NMR (CS2—CDCl3), δ: 100.00. 1H NMR
(CS2—CDCl3), δ: 0.89 (dd, 3 H, J = 7.3 Hz, J = 3.0 Hz); 1.61 (t,
3 H, Et, J = 7.3 Hz); 2.10 and 2.16 (both q, 4 H, J = 7.3 Hz, J =
7.9 Hz); 2.83 (s, 3 H, NMe); 3.90 (s, 1 H, CH of pyrrolidine);
4.06 (d, 2 H, J = 10.1 Hz); 4.29 and 4.96 (both s, 1 H each,
CH2 of pyrrolidine); 7.28 (d, 2 H, H arom., J = 21.2 Hz); 7.77
(br.s, 2 H, H arom.). 13C NMR (CS2—CDCl3), δ: 7.03; 10.16;
23.73; 28.40; 39.89 (NMe); 68.80; 68.57 (C(1)); 69.83; 76.73
(C(6)); 82.86, 121.86, 130.22, 133.26, 135.81 (C arom.); 136.57;
136.82; 139.52; 139.89; 140.14; 140.18; 141.53; 141.69; 141.81;
141.97; 142.05; 142.10; 142.15; 142.18; 142.27; 142.29; 142.57;
142.59; 142.69; 143.00; 143.10; 143.16; 144.38; 144.41; 144.60;
144.73; 145.15; 145.21; 145.25; 145.29; 145.32; 145.35; 145.46;
145.55; 145.79; 145.94; 146.01; 146.09; 146.21; 146.25; 146.29;
146.35; 146.39; 146.47; 146.65; 147.39; 153.05; 153.20.
MALDIꢀTOF MS, found: m/z 1019.43 [M]+. C74H22NO2PS.
Calculated: M = 1020.02.
We thank N. P. Evlampieva for measuring the dipole
moment of compound 7.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos 02ꢀ03ꢀ32900,
03ꢀ03ꢀ96248rTatarstan, 04ꢀ03ꢀ32287, and 05ꢀ03ꢀ32633)
and the Academy of Sciences of the Republic of Tatarstan.
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1ꢀ[4ꢀ(O,OꢀDiethylthiophosphoxy)phenyl]ꢀNꢀmethyl[60]fulꢀ
lereno[1,2ꢀc]pyrrolidine (8). Under the conditions described
above for the synthesis of compound 7, compound 8 was preꢀ
pared from fullerene C60 (0.216 g, 0.3 mmol), Nꢀmethylglycine
(0.080 g, 0.9 mmol), and compound 4 (0.165 g, 0.6 mmol) in a
yield of 0.088 g (31% based on consumed C60). UV, λmax/nm (ε):
258 (43700), 327 (13500), 430 (1700), 696 (300). IR, ν/cm–1
:
526, 744, 794, 802, 917, 1109, 1164, 1214, 1455, 1504, 1652.
31P NMR (CDCl3), δ: 61.9. 1H NMR (CDCl3), δ: 1.31 (t, 6 H);
2.81 (s, 3 H, NMe); 4.19 and 4.21 (both m, 4 H); 4.27 and 4.97
(both d, 2 H, CH2 of pyrrolidine); 4.93 (s, 1 H, CH of
pyrrolidine); 7.25 (d, 2 H, H arom.); 7.79 (br.s, 2 H, H arom.).
13C NMR (CDCl3), δ: 15.93; 40.03 (s, NMe); 65.15; 68.96
(C(1)); 69.92; 72.64 (C(6)); 82.87, 121.22, 130.39, 135.72,
135.91 (C arom.); 136.59; 136.97; 139.53; 139.94; 140.23;
140.27; 141.60; 141.75; 141.87; 141.98; 142.07; 142.11;
142.16; 142.22; 142.29; 142.61; 142.64; 142.76; 143.07; 143.21;
144.43; 144.47; 144.66; 144.78; 145.24; 145.29; 145.31; 145.35;
145.40; 145.42; 145.46; 145.58; 145.63; 145.81; 146.01; 146.09;
146.19; 146.21; 146.25; 146.28; 146.34; 146.38; 146.47; 146.65;
147.39; 153.04; 153.21; 153.95; 156.16. MALDIꢀTOF MS,
found: m/z 1021.71 [M]+. C73H20NO3PS. Calculated:
M = 1021.99.
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Received February 4, 2005;
in revised form February 17, 2006