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Polyhedral Rearrangements Involving Five- and Six-Coordinate Carbon.
CALIFORNIA UNIV LOS ANGELES DEPT OF CHEMISTRY
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Carbon atoms which are incorporated into polyhedral borane geometries exhibit properties consistent with their description as sequestered carbonium ions. In many carboranes and metallocarborane compounds, two of these positive carbon atoms occupy adjacent polyhedral vertices, and the large coulombic repulsive force generated by such positioning results in a tendency for the carbon atoms to migrate away from each other in a polyhedral rearrangement. The authors approach to the study of polyhedral heteroatom migrations has been to characterize the chemical consequences in terms of preferred heteroatom coordination, the various heteroatom effects on the activation energies for isomerization, and the effects of heteroatom positions on the physical properties of metallocarboranes. General rules of heteroatom migration have been developed for carboranes and metallocarboranes.
APPROVED FOR PUBLIC RELEASE