Reactions of C60 with phosphorus(III) amides
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 1, January, 2008
211
for the light quantum and solvation energies (the reactions
under discussion were carried out in the light).
or 2 (4.5 mg, 0.028 mmol) were dissolved in dry oꢀDCB (2 mL) and
the resulting solutions (0.2 mL) were added dropwise to the tube.
For experiments without access to air, the tube was preꢀevacuated.
To sum up, we found that fullerene C60 reacts with
phosphorus(III) derivatives to give unstable radical ion
salts. First, they are gradually oxidized with atmospheric
oxygen into phosphoric amides 7 and 8 and diamagnetic
fullerene derivatives (most likely, fullerene oxides and
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 05ꢀ03ꢀ
3
2418), the Federal Agency for Science and Innovations
(
State Contract No. 02.513.11.3209), and the Division
8
,15
dimers ). The formation of amides 7 and 8 is evident
from 3 P NMR data. For instance, immediately after the
mixing of fullerene with amide 2, the spectrum shows
of Chemistry and Materials Science of the Russian Acadꢀ
emy of Sciences (Program No. 7).
1
only a signal of amide 2 at δ 117.5. After 2 h, when the
P
References
content of salt 4 in the reaction mixture is highest (ESR
data), the 3 P NMR spectrum contains signals for amides
1
1
2
3
. A. Hirsch, M. Brettreich, Fullerenes: Chemistry and Reaction,
WileyꢀVCH Verlag GmbH and Co. KgaA, Weinheim, 2005,
2
and 8 in the ratio 2 : 1. After 11 h, the ratio of these
signals changes to 1 : 1; complete oxidation of amide 2
takes several days. Therefore, one can state that salts 3 and
4
25 pp.
. R. E. Douthwaite, M. L. H. Green, S. J. Heyes, M. J.
Rosseinsky, J. F. C. Turner, J. Chem. Soc., Chem. Commun.,
4
are formed from amides 1 and 2 rather than from
amides 7 and 8. Second, parts of salts 3 and 4 are most
likely converted into diamagnetic salt A, which is reꢀ
sponsible for the greenish color of the solution. The
formation of radical anions 5 and 6 may be explained by
several schemes. For instance, a pathway analogous to
1
994, 11, 1367.
. S. Bhattacharya, S. Banerjee, S. K. Nayak, S. Chattopadhyay,
A. K. Mukherjee, Spectrochim. Acta, Part A, 2004, 60, 1099.
4. S. Yamago, M. Yanagawa, H. Mukai, E. Nakamura, Tetraheꢀ
dron, 1996, 52, 5091.
. C. D. Stevenson, J. R. Noyes, R. C. Reiter, J. Am. Chem. Soc.,
2000, 122, 12905.
. D. Tumanskii, O. Kalina, Radical Reactions of Fullerenes and
Their Derivatives, Kluwer Academic Publishers, Dordrecht,
the Netherlands, 2002, 192 pp.
5
the addition of primary and secondary amines to fulleꢀ
rene16 should not be discarded. However, the specific
6
features of phosphorous amides should be taken into
•
+
17
consideration. Radical cations P(NR2)3
are known
to dimerize into stable dications. The process under study
can yield dication B. Being a strong electrophile, it can
attack the anion of salt A to give dication C. The latter
withdraws an electron from the fullerene radical anion to
form compounds 5 and 6, which are gradually oxidized
by atmospheric oxygen. Evidence for the formation of
the phosphorylated dication B could be provided by analoꢀ
gous experiments in the presence of alkenes. Such reacꢀ
tions are of interest for the roomꢀtemperature synthesis
of compounds with P—C bonds under mild conditions.
This will be the subject of our further investigations.
7
. E. E. Nifantiev, M. K. Grachev, S. Yu. Burmistrov, Chem. Rev.,
2
000, 100, 3755.
8. D. V. Konarev, R. N. Lubovskaya, Usp. Khim., 1999, 68, 19
[Russ. Chem. Rev., 1999, 68 (Engl. Transl.)].
9
. S. S. Eaton, G. R. Eaton, Appl. Magn. Reson., 1996, 11, 155.
0. J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996,
7, 3865.
1. D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151.
1
7
1
1
2. D. L. Lichtenberger, K. W. Nebesny, C. D. Ray, D. R.
Huffman, L. D. Lamb, Chem. Phys. Lett., 1991, 176, 203.
3. V. I. Nefedov, V. I. Vovna, Elektronnaya struktura organicheskikh
i elementorgnaicheskikh soedinenii [Electronic Structures of Orꢀ
ganic and Organoelement Compounds], Nauka, Moscow, 1989,
1
1
89 pp. (in Russian).
Experimental
1
1
4. L.ꢀS. Wang, Chem. Phys. Lett., 1991, 182, 5.
5. D. V. Konarev, S. S. Khasanov, G. Saito, A. Otsuka, R. N.
Lubovskaya, J. Mater. Chem., 2007, 17, 4171.
6. A. Skiebe, A. Hirsch, H. Klos, B. Gotschy, Chem. Phys. Lett.,
1
ESR spectra were recorded on a SE/Xꢀ2544 RadioPAN instruꢀ
ment. UV spectra were recorded on a Specord 61 NIR instrument.
P NMR spectra were recorded on a Bruker CXPꢀ100 instrument
36.48 MHz). oꢀDichlorobenzene (oꢀDCB) was dehydrated by disꢀ
1
3
1
994, 220, 138.
(
1
7. A. S. Romakhin, F. M. Palyutin, Yu. A. Ignatґev, E. V. Nikitin,
tillation over P O . Fullerene C was synthesized at the G. A.
2
5
60
Yu. M. Kargin, I. A. Litvinov, V. A. Naumov, Izv. Akad. Nauk
SSSR, Ser. Khim., 1990, 39, 664 [Bull. Acad. Sci. USSR, Div.
Chem. Sci., 1990, 39 (Engl. Transl.)].
8. V. V. Kormachev, N. S. Fedoseev, Preparativnaya khimiya
fosfora [Preparative Chemistry of Phosphorus], Perm, UrO RAN,
Razuvaev Institute of Organometallic Chemistry of the Russian
Academy of Sciences (Nizhny Novgorod). Amides 1 and 2 were
18
prepared as described earlier. Calculations were performed at the
Collective Computer Center of the Kazan Research Center of the
Russian Academy of Sciences.
1
1
992, p. 93 (in Russian).
Reactions of fullerene C60 with hexamethylꢀ and hexaethylꢀ
phosphorous triamides 1 and 2. Fullerene C60 (20 mg, 0.028 mmol)
was dissolved in dry oꢀDCB (2 mL). An aliquot (0.2 mL,
.8•10– mol L ) of the solution was placed in the quartz tube of
6
–1
2
Received 12 October 2006;
an ESR spectrometer. Freshly distilled amides 1 (7 mg, 0.028 mmol)
in revised form 21 November 2007