Structural comparison of alkylated derivatives of (bmmp-dmed)Ni and (bmmp-dmed)Zn |
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Authors: | Craig A. Grapperhaus Christopher S. Mullins Mark S. Mashuta |
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Affiliation: | Department of Chemistry, University of Louisville, 2320 So. Brook Street, Louisville, KY 40292, USA |
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Abstract: | The sulfur-alkylation of the nickel (1) and zinc (2) complexes of the dithiolate N2S2 ligand N,N′-bis-2-methyl-mercaptopropyl-N,N′-dimethylethylenediamine, H2(bmmp-dmed), have been investigated. Reactions with iodomethane yield [(Me-bmmp-dmed)Ni]PF6 (3), [(Me2-bmmp-dmed)NiI2] (4), and [(Me2-bmmp-dmed)ZnI]2[ZnI4] (5). Addition of iodoacetamide yields [(AA2-bmmp-dmed)Ni]I2 (6) and [(AA2-bmmp-dmed)Zn]I2 (7). Each of the metal-thioether products (3-7) have been characterized spectroscopically and by X-ray crystallography. Structural data is compared with that of the previously reported thiolato precursors 1 and 2. Sulfur-alkylation of 1 results in small relative changes in the nickel-sulfur bond distance, whereas for 2, the zinc-sulfur bond distance increases significantly, but is not cleaved. The difference between nickel and zinc is attributed to the release of a π*-bonding interaction between the metal and sulfur upon alkylation that compensates for the decreased σ-donor ability of the thioether in the case of nickel, but not for zinc. |
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Keywords: | Nickel Zinc S-alkylation Ligand centered reactivity |
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