Abstract

The structures of the allotropic modifications of phosphorus are briefly mentioned. The varying and interconvertible ring sizes of cyclopolyphosphines are considered, as is the use of these compounds as ligands in coordination chemistry. Aspects of structure and stability of cyclic phosphinoborines are followed by a discussion of phosphorus cage compounds; particular reference will be made to bond length variations in the bridging framework. Analogous variations are then considered for acyclic phosphorus–nitrogen compounds. Cyclophosphazenes form the major part of the lecture. Ring shapes, conformations of substituents, bond lengths and angles, basicities and other properties are discussed in some detail. Differences in ground state and perturbed state properties are considered. A comparison of structural changes accompanying protonation is made of two phosphazenes, where x-ray crystallographic data are available for the free bases and their conjugate acids. Finally, the current stage of theoretical concepts of bonding in these compounds is briefly surveyed.

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