REACTION OF NITROUS OXIDE
497
isolated and characterized [11]. It is also known that
a simple saturation with the nitrous oxide of a solu-
EXPERIMENTAL
2
+
Compounds Ib d, II, III were prepared along the
published procedures [17 19]. The process of
experiment is described with Ib complex. All the data
obtained are presented in the table.
tion of [Ru(NH ) (H O)]
resulted in a complex
3
5
2
2
+
[
Ru(NH ) (N O)]
where N O plays the role of
3 5 2
2
a ligand [12].
In the course of our study were obtained the cor-
responding furans in low to moderate yields in reac-
tions between the metal complexes Ib d, II, III and
nitrous oxide. We did not detect any nitrogen-contain-
ing compounds. Note that under the applied condi-
Reaction of N O with cobalt complex Ib. A solu-
2
tion of complex Ib (0.25 g, 0.4 mmol) in 10 ml of
benzene was charged into a reactor. On cooling the
bottom of the reactor we condensed thereto about
5
ml of nitrous oxide. The reaction was carried out
tions N O as potential oxygen donor in the reaction
2
for 6 h at 80 C. The reaction mixture was separated
by column chromatography on neutral alumina,
Brockmann activity II grade. By gradient elution with
hexane ethyl acetate mixture we separated and
identified the following compounds: initial complex
Ib (0.06 g, 0.1 mmol); 3,4-dimethyl-2,5-diphenyl-
furan (0.02 g, 0.08 mmol); triphenylphosphine oxide
of furan synthesis from rhodium complex II apparent-
ly is no better than commonly used molecular oxygen
or hydrogen peroxide [13]. Our data on reaction with
cyclopentadienyl compounds of cobalt Ib d should be
compared with investigation published by Wakatsuki
and Yamazaki [14]. There was studied thermal and
photochemical reaction of complexes Ia, b with
molecular oxygen that afforded as main products
dione complex IVa, b and dibenzoylstilbene (Va) or
(
0.08 g, 0.3 mmol).
REFERENCES
2
,3-dibenzoylbut-2-ene (Vb). The reaction scheme is
,
as follows:
1
. Leont ev, A.V., Fomicheva, O.A., Proskurnina, M.V.,
and Zefirov, N.S., Zh. Org. Khim., 1998, vol. 34,
no. 12, pp. 1864 1865.
2
3
4
5
. Kozikowski, A.P. and Wetter, H.F., Synthesis,
1
976, no. 9, pp. 561 590.
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J. Chem. Soc. A, 1968, no. 12, pp. 2886 2889.
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pp. 1707 1731.
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Commun., 1998, no. 7, pp. 751 752.
It was presumed [14] that the thermal reaction
70 C, 2 8 h) proceeded via dissociation of the
phosphine ligand followed by coordination of the
oxygen molecule at the vacant place in the cobalt
coordination sphere. As photochemical reaction
6. Haward, W.A., Waters, M., and Parkin, G., J. Am.
Chem. Soc., 1993, vol. 115, no. 11, pp. 4917 4918.
7. Yamamoto, A., Kitazume, S., Pu, L.S., and
Ikeda, S., J. Am. Chem. Soc., 1971, vol. 93, no. 2,
pp. 371 380.
(
(
1
under the light of a high pressure mercury lamp,
5 C, 8 9 h) the process may occur as phosphine
8. Arzoumanian, H., Nuel, D., and Sanchez, J., J. Mol.
Cat., 1991, vol. 65, no. 3, pp. L9 L11.
oxygen exchange or along the mechanism of [4+2]-
cycloaddition with participation of the forming singlet
oxygen acting as a reactive dienophile. With nitrous
oxide we failed to observe any dione complexes
apparently due to the used microamounts. However
it is well known that the reaction of but-2-ene-1,4-
9. Groves J.T., Roman J.S., J. Am. Chem. Soc., 1995,
vol. 117, no. 20, pp. 5594 5595.
10. Johnson, A.R., Davis, W.M., Cummins, C.C.,
Serron, S., Nolan, S.P., Musaev, D.G., and
Morokuma, K., J. Am. Chem. Soc., 1998, vol. 120,
no. 9, pp. 2071 2085.
11. List, A.K., Koo, K., Rheingold, A.L., and Hill-
house, G.L., Inorg. Chim. Acta., 1998, vol. 270,
no. 1 2, pp. 399 404.
diones with PPh under mild conditions affords the
3
corresponding furans [15]. We did not try to carry
out our reaction under photochemical conditions, but
it should be mentioned that N O photolysis was a
12. Diamantis, A.A., Sparrow, G.J., Snow, M.R., and
Norman, T.R., Austral. J. Chem., 1975, vol. 28,
no. 6, pp. 1231 1244.
2
convenient method for preparation of oxygen atoms
3
O( P) [16]. The mechanism of reactions between
cyclopentadienyl compounds of cobalt and nitrous
oxide requires further investigation.
13. Muller, E., Synthesis, 1974, no. 11, pp. 761 774.
14. Wakatsuki, Y. and Yamazaki, H., J. Organometal.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001