A NEW CLASS OF COMPLEXES POSSESSING COFACIALLY-ORIENTED, PLANAR, METAL-CONTAINING SUBUNITS - SYNTHESIS, CHARACTERIZATION, AND REACTIVITY OF[(MOO2)(2)(MU-O)](2-LINKED, CATECHOL-FUNCTIONALIZED, TETRAAZAMACROCYCLIC AND SALICYLIDENEAMINE COMPLEXES())

A new synthetic route to molecules that contain cofacially oriented, [ Mo2O5](2+)-bridged bis(catecholate) dianions is described. This synthe sis has been useful in the preparation of supermolecular molecules con taining catechol-functionalized, metalated macrocyclic [M-II(TAD(OH)(2 ))] (M = Co, Ni) and SALPHEN [M-II(R2R'(2)SALPHEN(OH)(2))] (M = H-2, M n, Fe, Co, Ni, Cu) ligands. Of the former, the (Bu4N)(2)[Mo2O5[Ni(TAD( O)(2))](2)] (7) complex has been structurally characterized. The compl ex crystallizes in the triclinic space group P (1) over bar with unit cell dimensions a 12.324(3) Angstrom, b = 17.740(4) Angstrom, c = 20.9 20(4) Angstrom, alpha = 108.79(3)degrees, beta = 98.20(3)degrees, and gamma = 103.12(3)degrees. The nearly-planar macrocyclic ligands are es sentially parallel, with a dihedral angle of 6.5(2)degrees. The Ni(1)- -Ni(2) separation in the anion is 3.938 Angstrom. The structure of (Bu 4N)(2)[Mo2O5[Cu(EtO(2)H(2)SALPHEN(O)(2))](2)] (19) has also been deter mined. This complex crystallizes in the monoclinic space group P2(1)/c , with unit cell dimensions a = 20.821(4) Angstrom, b = 23.133(5) Angs trom, c = 20.056(4) Angstrom, and beta = 117.71(3)degrees. The Cu(1)-- Cu(2) separation is 4.110 Angstrom, and the dihedral angle between SAL PHEN ''planes'' is approximately 9.7(1)degrees. Analytical and spectro scopic properties are provided. Reactions of these molecules with oxid ants and strongly coordinating ligands are presented. The ability of t he Fe-II and Co-II analogues of 19 to bind ligands such as O2- or S2- and O-2, respectively, in the ''pocket'' of the complex is described, and the products have been characterized. The synthesis and characteri zation of the unique ''mixed catecholate'' complexes (2)[Mo2O5((DBC)-B -t)(M-II((t)Bu(4)SALPHEN(O)(2)))] (M = H-2, Fe, Co, Ni, Cu) is describ ed, and comparisons between these latter systems and the bis(M-II-SALP HEN-catecholate) complexes are provided.