Complex Formation of Ni II , Cu II , Pd II , and Co III with 1,2,3,4‐Tetraaminobutane

Complex formation of the two tetraamine ligands (2 S ,3 S )‐1,2,3,4‐tetraaminobutane ( threo ‐tetraaminobutane, t tab) and (2 R ,3 S )‐1,2,3,4‐tetraaminobutane ( erythro ‐tetraaminobutane, e tab) with Co III , Ni II , Cu II , and Pd II was investigated in aqueous solution and in the solid state. For Ni II and Cu II , the pH‐dependent formation of a variety of species [M II x L y H z ] (2 x + z )+ was established by potentiometric titrations and UV/Vis spectroscopy. In sufficiently acidic solutions the divalent cations formed a mononuclear complex with the doubly protonated ligand of composition [M(H 2 L)] 4+ . An example of such a complex was characterized in the crystal structure of [Pd(H 2 t tab)Cl 2 ]Cl 2 ⋅H 2 O. If the metal cation was present in excess, increase of pH resulted in the formation of dinuclear complexes [M 2 L] 4+ . Such a species was found in the crystal structure of [Cu 2 ( t tab)Br 4 ]⋅H 2 O. Excess ligand, on the other hand, lead to the formation of a series of mononuclear bis‐complexes [M q (H x L)(H y L)] ( q + x + y )+ . The crystal structure of [Co(H e tab) 2 ][ZnCl 4 ] 2 Cl⋅H 2 O with the inert, trivalent Co III center served as a model to illustrate the structural features of this class of complexes. By using an approximately equimolar ratio of the ligand and the metal cation, a variety of polymeric aggregates both in dilute aqueous solution and in the solid state were observed. The crystal structure of Cu 2 ( t tab) 3 Br 4 , which exhibits a two‐dimensional, infinite network, and that of [Ni 8 ( t tab) 12 ]Br 16 ⋅17.5 H 2 O, which contains discrete chiral [Ni 8 ( t tab) 12 ] 16+ cubes with approximate T symmetry, are representative examples of such polymers. The energy of different diastereomeric forms of such complexes with the two tetraamine ligands were analyzed by means of molecular mechanics calculations, and the implications of these calculations for the different structures are discussed.