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Characterization of a kinetically stable, highly ordered, octameric form of lithium tert-butoxide and its
John F Allan1, Roger Nassar, Elizabeth Specht
1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
Abstract:
The controlled reaction of molecular oxygen with hydrocarbon solutions of tBuLi results in the unexpected formation of the octameric species [(tBuOLi)8], 18. Single-crystal X-ray diffraction studies indicate that the connectivity within 18 corresponds with the fusion of two face-opened tetrameric cubanes. Cryoscopic studies establish the stability of the octamer in benzene solution, but heating results in aggregate rearrangement to the commonly found prismatic hexameric form, 16. Theoretical calculations confirm that the hexameric form is the thermodynamically favored aggregate.
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To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
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