906
LEONT’EV et al.
Li/Me3SiCl/MCln are capable to effect conversion of
of nitrogen to tris(trimethylsilyl)amine (I), using as
substrates molecular nitrogen, air, or N2O. Such re-
action with nitrogen has first been described by Shiina
[6], and our results are in general agreement with his
data. Oxygen reduces the yields of the nitrogen reduc-
tion reactions by destroying the reductive systems
[9, 10]. In our case the effect of oxygen on the nitro-
gen-fixing systems is that it reduces the activity of
the transition metal compounds, thus limiting the
nitrogen conversion by 0.5 0.6. Interesting results
were obtained in experiments with nitrogen(I) oxide.
In the systems including CoCl2 and Cp2TiCl2,
twice as much amine I is formed, when the source of
nitrogen is N2O rather than molecular nitrogen. We
consider this result as clear evidence against primary
formation of nitrogen from nitrogen(I) oxide and in
favor of another mechanism of tris(trimethylsilyl)-
amine formation in this case. More probably that here
coordination and activation of N2O with transition
metal complexes occurs, like with the ruthenium
complexe [Ru(NH3)5(N2O)]2+ [4]. After that dinitro-
gen complexes are formed under the action of chloro-
trimethylsilane and with N O bond cleavage, which
further undergo reductive silylation. Oxygen transfer
from nitrogen is facilitated by the high affinity of
oxygen to silicon and is accompanied by abundant
polysiloxane formation. The poor activity of nitrogen-
fixing systems on the basis of chromium(III) and
iron(III) chlorides with respect to nitrogen(I) oxide is
probably associated with the intrinsic oxidative ac-
tivity of N2O.
methylsilyl)amine (I) was synthesized by the proce-
dure described in [11].
Reaction of air, nitrogen, and nitrogen(I) oxide
with nitrogen-fixing systems Li/Me3SiCl/MCln.
Transition metal salt, solvent, and chlorotrimethyl-
silane were placed in a Schlenk vassel (50 ml) filled
with one of the gases, and the mixture was stirred
under the same gas, filtered, the precipitate was
washed with hexane, and the filtrate was reduced to
required volume and analyzed by GLC.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 99-03-
33055).
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 6 2001