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Ionization Potentials of Silenes (R2SidCR2). Experiment Michael Bendikov, Bahman Solouki, Norbert Auner,*, and Yitzhak Apeloig*,

Summary: Ionization Potentials of Silenes (R2SidCR2). Experiment
and Theory
Michael Bendikov, Bahman Solouki, Norbert Auner,*, and Yitzhak Apeloig*,
Department of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum
Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel, and Institut fušr
Anorganische Chemie der Johann Wolfgang Goethe Universitašt Frankfurt am Main,
Marie-Curie Strasse 11, 60439 Frankfurt, Germany
Received September 17, 2001
We have measured the photoelectron (PE) spectra of two new silenes: the kinetically stable
long-lived silene t-BuMe2Si(Me3Si)SidAd (3) and a transient silene which was generated in
the gas phase by pyrolysis of the corresponding precursor. Previously, PE spectra of only
two transient silenes have been reported. The ionization potential (IP) of 3 is 6.9 eV, 2 eV
lower than that of H2SidCH2. Quantum-mechanical calculations reproduce quite well the
experimental IPs. The trends in IP1 are well-reproduced by calculations of the silene's HOMO,
even at the HF/6-31G(d)//HF/6-31G(d) level of theory. However, the correct absolute IPs are
reproduced quantitatively (to within 0.1-0.2 eV) only at a higher theoretical level, such as
ROVGF/6-311+G(2df,p), MP4/6-311+G(2df,p), or B3LYP/6-311+G(2df,p). Lower level ab
initio calculations, such as ROVGF/3-21G(d) and ROVGF/6-31G(d), reproduce the trends in
the IPs. The theoretical and experimental data show that the effect of substituents on the
HOMO energy of silenes is slightly smaller than in the corresponding alkenes. Disilyl


Source: Apeloig, Yitzhak - Department of Chemistry, Technion, Israel Institute of Technology


Collections: Chemistry