Synthesis of Transannular- and Spiro-Substituted Cyclotriphosphazenes: X-ray Crystal Structures of 1, 1-[N₃P₃(OCH₂CF₃)4(O₂C₁₂H₈)], 1, 3-[N₃P₃(OCH₂CF₃)₄(O₂C₁₂H₈)], l, l-[N₃P₃(OCH₂CF₃)₄(O₂C₁₀H₆)], and l, 3-[N₃P₃(OCH₂CF₃)₄(O₂C₁₀H₆)]

A cyclic triphosphazene with four trifluoroethoxy side groups and two nongeminal chlorine atoms, 1, 3-[N₃P₃(OCH₂-CF₃)₄C1₂), reacts with difunctional alcohols or amines to give transannular derivatives. Examples of the difunctional reagents used include catechol, 2, 2'-biphenol, 1, 8-dihydroxynaphthalene, 1, 8-diaminonaphthalene, 1, 3-propanediol, 1, 3-diaminopropane, and 2, 2'-dilithiobiphenyl. These are the first examples of transannular-bridged structures derived from aromatic diols or diamines. The analogous spirocyclic derivatives were prepared directly from hexachlorocyclotriphosphazene via a simple two-step reaction pathway using the same difunctional reagents. The solid-state structures of 1, 1-and l, 3-[N₃P₃(OCH₂CF₃)₄(O₂Ci₂H₈)] and 1, 1-and l, 3-[N₃P₃(OCH₂CF₃)₄(O₂CioH6)] were determined by X-ray diffraction, and the effects of transannular versus spiro substitution on the planarity of the phosphazene ring and (by implication) on the phosphazene ring strain were studied. These compounds are starting materials for phosphazene ring-expansion or ring-opening polymerization reactions.