The classical valence isomers of benzene, namely Dewar-benzene, benzvalene, and prismane, are well known. Phospha-, azaphospha-, and diphosphabenzenes as well as the Dewar and benzvalene derivatives with the same combinations of heteroatoms are described in this review. Phospha-, azaphosphaprismanes are now also known and discussed. Starting materials for these compounds are the kinetically stabilized cyclobutadienes, azacyclobutadienes, as well as the short-lived 1,3-diphosphacyclobutadienes which, upon reaction with phosphaalkynes, provide an access to the mentioned classes of compounds (Scheme 1).
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