Dinuclear nickel(II) complexes of the ligands 2,6-bis[bis((2-benzimidazolylmethyl)amino)methyl]-p-cresol (bbapOH), N,N,N’,N’-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane (tbpOH), N-methyl-N,N’,N’-tris(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane (m-tbpOH) and 1-[N,N-bis(2-benzimidazolylmethyl)-amino]-3-[2-(3,5-dimethyl-1H-pyrazol-1-yl)ethoxy]-2-hydroxypropane (bpepOH) were prepared in order to model the active site of urease. The novel asymmetric structures of the dinuclear complexes were characterized by X-ray structure analysis. The complex [Ni-2(bbapO)(ClO4)(H2O)(MeOH)](ClO4)(2) . Et(2)O 1, crystallizes in the monoclinic space group P2(1)/c, with a = 10.258(2) Angstrom, b = 19.876(3) Angstrom, c = 25.592(4) Angstrom, and beta = 97.12(2)degrees. The nickel ions in 1 are bridged by the phenoxy donor of the ligand and a perchlorate anion. The complexes [Ni-2(tbpO)(MeCOO)(H2O)](ClO4)(2) . H2O . Et(2)O, 2, [Ni-2(m-tbpO)(PhCOO)(EtOH)(2)](ClO4)(2) . EtOH, 3, and [Ni-2(bpepO)(MeCOO)(H2O)(2)](ClO4)(2) . H2O . Et(2)O . 2EtOH 4, also crystallize in the monoclinic crystal system with the following unit cell parameters : 2, C2/c, a = 35.360(13) Angstrom, b = 10.958(3) Angstrom, c = 24.821(10) Angstrom, beta = 103.55(3)degrees; 3, Cc, a = 14.663(5) Angstrom, b = 32.630(13) Angstrom, c = 9.839(3) Angstrom, beta = 92.49(2)degrees; 4, C2/c, a = 27.689(13) Angstrom, b = 12.187(5) Angstrom, c = 31.513(14) Angstrom, beta = 115.01(3)degrees. The dinuclear centers of all these complexes are bridged by the alkoxy donor of the ligand and a carboxylate function. Compounds 2 and 3 have one of the nickel ions in a five-coordinated, trigonal bipyramidal coordination environment and thus show a high structural similarity to the dinuclear active sire of urease from Klebsiella aerogenes. Furthermore, their magnetic and spectroscopic properties were determined and related to those of the urease enzymes. Activity toward hydrolysis of test substrates (4-nitrophenyl)urea, 4-nitroacetanilide, 4-nitrophenyl phosphate or bis(4-nitrophenyl) phosphate by the dinuclear complexes were examined by UV spectroscopic measurements.