三価の超原子価ヨウ素化合物とクラウンエーテルとの錯体の合成とその反応

概要

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In this review, we show that intermolecular hypervalent I(III)…O interactions play an essential role in the complexation of organo-λ3-iodanes with crown ethers. In addition to the well-known driving force for the complexation of crown ethers, ion-dipole interaction, and hydrogen bonding interaction, our result provides a new class of interaction in supramolecular chemistry of crown ethers. Both solid state structure analysis and solution chemistry indicate that diaryl-, 1-alkenyl(phenyl)-, 1-alkynyl(phenyl)-, and hydroxy(phenyl)-λ3-iodanes form stable complexes with 18-crown-6 through hypervalent I(III)…O interactions. The complexation not only increases the stability of these hypervalent λ3-iodanes but also holds its high reactivity toward nucleophiles. The complex of hydroxy(phenyl)-λ3-iodanes with 18-crown-6 serve as versatile oxidizing agents, especially in water.