Realization of unusual ligand binding motifs in metalated container molecules: synthesis, structures, and magnetic properties of the complexes [(LMe)Ni2(mu-L')]n+ with L'=NO3-, NO2-, N3-, N2H4, pyridazine, phthalazine, pyrazolate, and benzoate.

A series of dinickel(II) complexes with the 24-membered macrocyclic hexaazadithiophenol ligand H(2)L(Me) was prepared and examined. The doubly deprotonated form (L(Me))(2-) forms complexes of the type [(L(Me))Ni2II(mu-L')](n+) with a bioctahedral N(3)Ni(II)(mu-SR)(2)(mu-L')Ni(II)N(3) core and an overall calixarene-like structure. The bridging coordination site L' is accessible for a wide range of exogenous coligands.

First Examples of Dinickel Complexes Containing the N(3)Ni(&mgr;(2)-SR)(3)NiN(3) Core. Synthesis and Crystal Structures of [L(2)Ni(2)][BPh(4)](2) and [L(3)Ni(2)][BPh(4)](2) (L = 2,6-Di(aminomethyl)-4-tert-butyl-thiophenolate).

A coordinatively unsaturated dinuclear Ni(II) complex of the tridentate ligand 2,6-di(aminomethyl)-4-tert-butyl-thiophenol (HL) has been synthesized and investigated in the context of ligand binding and oxidation state changes. The starting complex [L(2)Ni(2)][BPh(4)](2) (1) is readily prepared from NaL, NiCl(2).6H(2)O, and NaBPh(4) in methanol.