Physics
Scientific paper
Jun 2009
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009mss..conferb05l&link_type=abstract
"International Symposium On Molecular Spectroscopy, 64th Meeting, Held 22-26 June, 2009 at Ohio State University. http://molspec
Physics
Radicals And Ions
Scientific paper
Transition metal bis(arene) sandwich complexes may adopt eclipsed or staggered conformations due to the aromatic ring rotations about the metal-arene axis. In this study, the group VI (Cr, Mo, and W) metal bis(toluene) complexes are synthesized in a laser-ablation molecular beam source, and their rotational conformers are identified by pulsed-field-ionization zero-electron-kinetic-energy (ZEKE) spectroscopy. For Cr-bis(toluene), the ZEKE spectrum shows three distinctive vibrationless (0-0) transitions between the ground electronic states of the neutral and ionic complexes at 42739(5), 42745(5), and 42805(5) cm^{-1}, corresponding to ionization energies of 180°, 60°/120°, and 0° rotamers. In addition, the spectrum exhibits metal-toluene bending (164, 180, 196, and 223 cm^{-1}) and stretching (278 and 291 cm^{-1}) frequencies of these rotamers. The ground electronic states of the 0° and 180° rotamers are ^{1}A_1 (C_{2v}) and ^{1}A_g (C_{2h}) in the neutral form and ^{2}A_1 (C_{2v}) and ^{2}A_g (C_{2h}) in the ionized form, respectively. For the 60° and 120° rotamers, the ground states of the neutral molecules are ^{1}A (C_2), and those of the corresponding ions are ^{2}A (C_2). Through the variation of the molecular beam conditions, the eclipsed conformer (0°) is determined to be more stable than the staggered ones (180°, 120°, and 60°). Similarly, multiple conformers are identified for the Mo and W complexes.
B.S. Sohnlein, S. Li, and D.S. Yang, J. Chem. Phys. 123, 214306 (2005)
B.S. Sohnlein and D.S. Yang, J. Chem. Phys. 124, 134305 (2006)
S.Y. Ketkov, H.L. Sezle, and F.G.N. Cloke, Angew. Chem. Int. Ed. 46, 7072 (2007)
Kumari Sudesh
Lee Jung Sup
Yang Dong-Sheng
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