Structure of Metal Alkoxides

Abstract

THE polymeric co-ordination compounds are important in inorganic chemistry. Structural studies of these compounds have recently revealed the presence of cyclic and macromolecular1 structural types, which previously were counted as the distinguishing features of organic chemistry. Metal alkoxides are an important set of co-ordination compounds synthesized about ten years ago2,3. Polymerization and complex formation take place in the alkoxides due to the tendency of the metal atom to attain maximum covalency. The evidence for polymerization in the alkoxides has been almost wholly based on determination of their molecular weight4. The structural determination of some Group IV and Group V metal alkoxides has been taken up5, and on X-ray evidence it has already been conclusively shown6 that in case of tantalum monoethoxide tetra tertiary butoxide the nature of the structural repeat unit is dimeric. I wish to report here that titanium tetra isobutoxide with isobutanol of addition, zirconium tetra isopropoxide with isopropanol of addition and hafnium tetra isopropoxide with isopropanol of addition, have been found to be dimeric, on the basis of X-ray crystallographic evidence; they exist as two octahedra of oxygens around the metals sharing an edge. Thus complex alkoxides of Group IV and the alkoxides of Group V behave structurally similarly; they illustrate the concept of bondability7 of an atom which is replacing the concept of valency. The details of this work will be published elsewhere. The significance of this work becomes evident in the context of the previous work and the recent extensions in the field8–11.

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IMAM, S. Structure of Metal Alkoxides. Nature 206, 1146–1147 (1965) doi:10.1038/2061146a0

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