title: Phosphorus-based p-tert-butylcalix[5]arene ligands.
abstract: New calix[5]arene trivalent phosphorus derivatives have been synthesized which should be excellent ligands with which 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 moieties into the calix[5]arene framework to give calix[5](PR)2(OH) (1, R = Me2N; 2, R = Ph). Further treatment of 1 with 4 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 2 have approximate cone conformations while 3 has an approximate 1,2-alternate conformation. The orientations of the phosphorus lone pairs and oxygen atoms in all derivatives provide a framework for both soft and hard ligand interactions within the calix[5]arene.
authors.affiliation: Department of Chemistry, Southern Methodist University, Dallas, Texas 75275-0314, USA.
authors.forename: Paul
authors.initials: P
authors.lastname: Sood
authors.forename: Mohan
authors.initials: M
authors.lastname: Koutha
authors.forename: Maomian
authors.initials: M
authors.lastname: Fan
authors.forename: Yaroslav
authors.initials: Y
authors.lastname: Klichko
authors.forename: Hongming
authors.initials: H
authors.lastname: Zhang
authors.forename: Michael
authors.initials: M
authors.lastname: Lattman