Zinc/nickel exchange and ligand cannibalism in N2S2O(1,2) donor ligand sets

To explore the displacement of Zn(2+) by Ni(2+) from within N-, S-, and O-chelate ligands, (N-(3-thiabutyl)-N'-(3-thiapentaneoate)-1,4-diazacycloheptane)zinc(II), Zn-1'-Ac, and 1,4-diazacycloheptane-1,4-diylbis(3-thiapentanoato) zinc(II), Zn-1'-Ac(2), were reacted with Ni(BF(4))(2) in a methanol solution and were found to yield, in both cases, the bright blue, hexa-coordinate Ni-1'-Ac(2) metal-exchanged product. The latter conditions imply an intact-ligand unwrapping process as the hexadentate N(2)S(2)O(2) ligand is transferred from zinc to nickel. The former involves transfer of the pentadentate N(2)S(2)O ligand generating a green, penta-coordinate nickel intermediate which engages in CH(2)CO(2) fragment scavenging from a second zinc unit. This conclusion is supported by the observed analogous reformulation of the stable Zn-1'-Ac complex into Zn-1'-Ac(2) and the dithiolato [Zn-1'](2) dimer. To our knowledge, this is a rare (possibly the first) example of cannibalism reported in such ligand systems. The M-1'-Ac(2) complexes were characterized by X-ray diffraction and compared to the directly synthesized products.