ELECTRONIC SPECTROSCOPY OF JET-COOLED HALF-SANDWICH ORGANOMETALLIC COMPLEXES $CaC_{5}H_{5}$, $CaC_{5}H_{4}CH_{3}$ and $CaC_{4}H_{4}N$
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Date
1992
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Ohio State University
Abstract
Laser excitation and dispersed fluorescence spectra of jet-cooled open-faced organometallic complexes, $CaC_{5}H_{5}$, $CaC_{5}H_{4}CH_{3}$ and $CaC_{4}H_{4}N$ will be discussed. The electronic structure of these molecules can best be described as $Ca^{+}$ being perturbed by $R^{-} (R = C_{5}H_{5}$, $C_{5}H_{4}CH_{3}$ and $C_{4}H_{4}N$). The electronic transitions observed here are essentially metal-centered. Their electronic spectra show extensive vibrational structure arising from excitation of skeletal and intra-ring modes. From this structure, we are able to determine the binding site of $Ca^{+}$, i.e. above the ring in a pentahapto bonding fashion. The electronic spectra of $CaC_{5}D_{5}$ and $CaC_{4}D_{4}N$ are also presented here to provided information about ``pure” hydrogenic vibrations in $CaC_{5}H_{5}$ and $CaC_{4}H_{4}N$. In the case of $CaC_{5}H_{4}CH_{3}$ methyl torsional bands are observed, from which the harrier to methyl free rotation and the change in conformation of the methyl group on $\tilde A-\tilde X$ excitation are determined.
Description
Author Institution: Laser Spectroscopy Facility, The Ohio State University; Department of Chemistry, University of Leicester