ROTATIONAL SPECTRA AND HYPERFINE STRUCTURE FOR A TITANIUM SANDWICH COMPLEX, C$_5$H$_5$TiC$_7$H$_7$
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Date
2005
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Publisher
Ohio State University
Abstract
\begin{wrapfigure}[9]{R}{4CM} \vspace{-0.6cm} \hspace*{-0.1cm} \epsfig{file=cpti8.eps} \end{wrapfigure} Microwave spectroscopy measurements and density functional theory calculations are reported for the cyclopentadienylcycloheptatrienyltitanium complex, C$_5$H$_5$TiC$_7$H$_7$. This appears to be the first microwave work on a complex containing the cycloheptatrienyl ligand. Rotational transition frequencies for this symmetric-top complex were measured in the 4-13 GHz range using a Flygare-Balle-type pulsed beam spectrometer. The spectroscopic constants obtained for the normal isotopomer are B= 771.78907(38), D$_J$= 0.0000295(41), and D$_{JK}$= 0.001584(73) MHz. The quadrupole hyperfine splittings for C$_5$H$_5$$^{48}$TiC$_7$H$_7$ were clearly observed, and eQq$_{aa}$= 18.432(90) MHz. Analysis of the rotational constants indicates that bond lengths in the gas phase are about 0.02\AA\ longer than those reported for the solid-state X-ray structure. The calculated Ti-C bond lengths are shorter for the C$_7$H$_7$ ligand (r(Ti-C)=2.21\AA) than for the C$_5$H$_5$ ligand (r(Ti-C)=2.34\AA), and the C$_7$H$_7$ H atoms are displaced 0.15\AA\ out of the C7 plane, toward the Ti atom.
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{Supported by THE NATIONAL SCIENCE FOUNDATION CHE0304969
Author Institution: Department of Chemistry, University of Arizona, Tucson, AZ 85721
Author Institution: Department of Chemistry, University of Arizona, Tucson, AZ 85721