9
(a) S. Elbel and E. Niecke, J. Chem. Soc., Dalton. T rans., 1985,
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was e†ected inside the ionization chamber of the UV-PES
spectrometer equipped with an internal heater device. The
pressure of the ionization chamber was 10~5 mbar without
sample. The Ðrst experiment, denoted ““internal thermolysisÏÏ,
allowed the analysis of both species with short lifetimes and
their decomposition products. The second system was an
apparatus external to the spectrometer, which allowed a
separate product study. Thermolysis was performed in a
vacuum device (pressure in the oven: 10~5 mbar without
sample) connected to the spectrometer. In this case only the
stable and volatile species were characterized after cryogenic
distillation. Unstable compounds decomposed and/or poly-
merized because of the long distance between the oven and
the ionization head. Thermolysis temperatures varied between
300 and 1300 K depending on the compound being studied.
Compounds 1b and 2a were obtained by previously
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described
methods.27,28
2b
was
prepared
from
(Me tBuSi) NLi and AsCl as described for 2a.29
2
2
3
19 M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G.
Jonhson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Peters-
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Acknowledgements
Financial support of this work by the CNRS (France) is grate-
fully acknowledged. We also thank the Institut du
Developpement de Ressources en Informatique ScientiÐque
(IDRIS, Orsay, France), administered by the CNRS, for the
calculation facilities, and Dr Gijs Schaftenaar for allowing us
to use his graphics program Molden.30
20 W. J. Hehre, L. Radom, P. v. R. Schleyer and J. A. Pople, Ab
Initio Molecular Orbital T heory, John Wiley and Sons, New
York, 1986.
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3
[s, 12H, Si(CH ) ], 0.90 [s, 18H, tBu]; anal. calc. for
3 2
C
H
AsCl NSi : C 36.92, H 7.75; found C 36.80, H 7.80%.
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938
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