Phosphorus-based p-tert-butylcalix[5]arene ligands

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 HCI gives calix[5](PCI)(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.