Titanium and Zirconium Complexes of a Phosphorus-Containing <i>p-tert-</i>Butylcalix[5]arene Ligand: Importance of Metal and Conformation on Ligand/Metal Binding

Binding of a calix[5]arene containing a single phosphorus ligand and three hydroxyl groups, calix[5]PNMe2(OH)3, 1, toward titanium and zirconium is investigated to yield insight into the factors that determine the strength of the phosphorus/metal interaction within the constraint of the calix[5]arene. Treatment of 1 with tetrakis(dimethylamino)titanium yields three complexes, 4a, 4b, and 4c, each of which shows the loss of 3 mol of dimethylamine in the reaction with the titanium bound to three oxygens. Treatment of 1 with tetrakis(diethylamino)zirconium proceeds similarly, although only two products, 5a and 5b, were isolated. X-ray structures of the products were obtained. Complexes 4a and 5a show similar geometries, with the calix[5]arene in an approximate cone conformation and the phosphorus lone pair directed toward the metal. The P···M distances are, however, markedly different: 3.69 Å in 4a and 3.18 Å in 5a, the former indicative of no interaction and the latter a weak one. Complexes 4b and 5b each are dimers, featuring a planar four-membered M−O−M−O ring; however, the titanium is five-coordinate in 4b with no phosphorus/metal bond, while the zirconium in 5b is six-coordinate with a P−Zr distance of 2.95 Å. Complex 4c is monomeric with the calix[5]arene in an approximate 1,2-alternate conformation with a P···Ti distance of 2.90 Å. The two most significant aspects controlling the phosphorus/metal contact are the metal, with the larger zirconium showing stronger interaction, and the calix[5]arene conformation, with the cone conformation showing the weaker interaction.