TRANSITION-METAL RIMMED CALIXRESORCINARENE COMPLEXES

A bowl-shaped calixresorcinarene 1 has been derivatized to incorporate four phosphonite units to give a phosphonitocavitand 2 and eight phos phinite units to give phosphinito-calixresorcinarene 3. These derivati ves have been used as multidentate ligands to incorporate transition m etals on the upper rim of the calixresorcinarene bowl. Several gold(I) complexes and platinum(II) complexes have been synthesized. The chlor ogold(I) complex of 2, 2(AuCl)4, was characterized by an X-ray structu re determination [crystal data: C84H68Au4Cl4P4O8.0.5CH(2)Cl(2).2.5CH(3 )CN.H2O, fw = 2422.16, triclinic, P $($) over bar$$ 1, a = 15.271(5) A ngstrom, b = 28.399(8) Angstrom, c = 11.060(5) Angstrom, alpha = 93.40 (3)degrees, beta = 111.21(3)degrees, gamma = 98.41(2)degrees, V = 4390 .8 Angstrom(3), Z = 2, R = 0.0534, R(w) = 0.0504]. This complex is sho wn to contain three AuCl units around the upper rim of the bowl with t he fourth AuCl unit-folded inside the cavity. The gold(I)-rimmed bowl forms inclusion complexes with amines and alkali metal cations but not with other potential substrates.