ABSTRACT
Treatment of a bis(phenylphosphonite)calix[5]arene ligand with either palladium(II) chloride or 1,5-cyclooctadieneplatinum(II) chloride yields square planar metal complexes in which the two phosphorus atoms bind cis to the MCl(2) moiety (M = Pd, Pt). Chloride was removed from the palladium complex to open a coordination site at the metal for catalysis. The chloride removal resulted in a rare and unexpected η(6) coordination of an arene to the metal. The reaction is reversible upon addition of tetra-n-butyl ammonium chloride.
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.
