Unexpected Ring Expansion of a Four-Membered Cyclophosphazane

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• 作者：Serap Beşli ; Ceylan Mutlu Balcı ; Hakan Cantürk ; Semih Doğan ; Fatma Yuksel ; Christopher W. Allen
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 15, 2016
• 年：2016
• 卷：55
• 期：16
• 页码：7832-7834
• 全文大小：283K
• 年卷期：0
• ISSN：1520-510X

文摘

Nucleophilic substitution reactions of the N(R),N(R)-spiro-bridged octachlorobis(cyclotriphosphazene), N₃P₃Cl₄[N(CH₂)₅CH₃]₂N₃P₃Cl₄ (1), with sodium salts of alcohols (1,3-propanediol, 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, and phenol) give ansa products (2–4) via an unexpected rearrangement. These products were characterized by elemental analysis, mass spectrometry, and ¹H and ³¹P NMR spectroscopy. The molecular structures of compounds 3 and 4 were also established by X-ray crystallography. This new class of phosphazene structures consists of three fused P₃N₃ rings that arise from expansion of the four-membered phosphazane ring in 1 to a six-membered N₃P₃ ring during alcoholysis reactions.