Phosphorus-Based p-tert-Butylcalix[5]arene Ligands

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• 作者：Paul Sood ; Mohan Koutha ; Maomian Fan ; Yaroslav Klichko ; Hongming Zhang ; and Michael Lattman
• 刊名：Inorganic Chemistry
• 出版年：2004
• 出版时间：May 3, 2004
• 年：2004
• 卷：43
• 期：9
• 页码：2975 - 2980
• 全文大小：183K
• 年卷期：v.43,no.9(May 3, 2004)
• ISSN：1520-510X

文摘

New calix[5]arene trivalent phosphorus derivatives have been synthesized which should be excellent ligands withwhich to study and control the interaction of a ligand atom with a metal. The larger cavity of the calix[5]arene(compared to calix[4]arene) provides a good balance between constraint and flexibility. Treatment of p-tert-butylcalix[5]arene with 2 equiv of either tris(dimethylamino)phosphine or dichlorophenylphosphine inserts two RP moietiesinto the calix[5]arene framework to give calix[5](PR)₂(OH) (1, R = Me₂N; 2, R = Ph). Further treatment of 1 with4 equiv of HCl gives calix[5](PCl)₂(OH) (3). Heating a solution of the monophosphorus compound calix[5](PNMe₂)(OH)₃ (4) releases dimethylamine to yield both monomeric calix[5](P)(OH)₂ (6) and dimeric {calix[5](P)(OH)₂}₂ (7),the latter having a tubelike geometry. X-ray crystallographic studies confirm the structures and show that 1 and 2have approximate cone conformations while 3 has an approximate 1,2-alternate conformation. The orientations ofthe phosphorus lone pairs and oxygen atoms in all derivatives provide a framework for both soft and hard ligandinteractions within the calix[5]arene.