Zinc/Nickel exchange and ligand cannibalism in N2S2O1,2 donor ligand sets
| Autor: | Elky Almaraz, Marcetta Y. Darensbourg, William S. Foley, Jason A. Denny, Nattamai Bhuvanesh, Joseph H. Reibenspies |
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| Rok vydání: | 2009 |
| Předmět: |
Models
Molecular Nitrogen Chemistry Ligand Dimer Inorganic chemistry Molecular Conformation Cannibalism chemistry.chemical_element Zinc Crystallography X-Ray Ligands Molecular conformation Oxygen Inorganic Chemistry Nickel Crystallography chemistry.chemical_compound Yield (chemistry) Methanol Sulfur Chelating Agents |
| Zdroj: | Dalton Transactions. :9496 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/b914422f |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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