Isolation, characterization, and reaction of activated iodosylbenzene monomer hydroxy(phenyl)iodonium ion with hypervalent bonding: supramolecular complex PhI+OH.18-crown-6 with secondary I...O interactions.
Isolation, characterization, and reaction of activated iodosylbenzene monomer hydroxy(phenyl)iodonium ion with hypervalent bonding: supramolecular complex PhI+OH.18-crown-6 with secondary I...O interactions.
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DOI：
10.1021/ja0377899
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发表时间：
2003-10
影响因子：
15
通讯作者：
M. Ochiai;K. Miyamoto;M. Shiro;Tomoyuki Ozawa;K. Yamaguchi
中科院分区：
文献类型：
--
作者：
M. Ochiai;K. Miyamoto;M. Shiro;Tomoyuki Ozawa;K. Yamaguchi
本文报道了活性物质羟基（苯基）碘离子的分离、表征及其与高价键的反应。在等摩尔18-冠-6存在下，碘基苯与HBF(4)-Me(2)O在二氯甲烷中反应得到羟基-(3)-碘配合物PhI(OH)BF(4)。18冠6为稳定的黄色棱镜。x射线结构分析表明，碘（III）与相邻的3个氧原子（18-crown-6）紧密接触，氢键OH形成。与未络合的PhI(OH)BF(4)相比，O（冠醚）将增加配合物的稳定性。冠醚配合物是高活性的，甚至在水中也是一种多功能氧化剂：因此，配合物在温和的条件下可以发生各种官能团的氧化转化，如烯烃、炔烃、烯酮、硅烯醇醚、硫化物和酚。
The isolation, characterization, and reaction of the active species hydroxy(phenyl)iodonium ion with hypervalent bonding are reported. Reaction of iodosylbenzene with HBF(4)-Me(2)O in the presence of equimolar 18-crown-6 in dichloromethane afforded the hydroxy-lambda(3)-iodane complex PhI(OH)BF(4).18-crown-6 as stable yellow prisms. X-ray structure analysis indicated that both the close contacts between the iodine(III) and the three adjacent oxygen atoms of 18-crown-6, and the hydrogen bonding OH.O(crown ether) will be responsible for the increased stability of the complex as compared to the uncomplexed PhI(OH)BF(4). The crown ether complex is highly reactive and serves as a versatile oxidant even in water: thus, the complex undergoes oxidative transformations of a variety of functional groups such as olefins, alkynes, enones, silyl enol ethers, sulfides, and phenols under mild conditions.