INOR 658 |
| The chemistry of thiolato-nickel complexes is of fundamental importance in biological processes. Here, we report different reactivity for triphenylmethyl- and phenyl-thiolato nickel(II) complexes having the PhTttBu ligand (PhTttBu = phenyltris((t-butylthio)methyl)borate). The addition of Ph3CSH to a CHCl3 solution of [PhTttBu]Ni(NO3) (1) in the presence of Et3N led to a rapid color change from yellow green to dark violet. The resulting triphenylmethyl-thiolato nickel(II) complex, [PhTttBu]Ni(SCPh3) (2), was not thermally stable and the decomposition of 2 resulted in the formation of a µ-η2:η2-disulfido dinickel(II) complex, [PhTttBu]2Ni2(S2) (3), via C-S bond cleavage. In contrast, PhSH was added to a pentane solution of 1 in the presence of Et3N at -40 °C, producing a phenyl-thiolato nickel(II) complex, [PhTttBu]Ni(SPh) (4). Thermal decomposition of 4 at room temperature resulted in unexpected nickel alkylation, giving [PhBttBuSPh]Ni(CH2SBut) (5) where PhBttBuSPh is phenylbis((t-butylthio)methyl)(phenylthio)borate. The complexes, 1, 2, 3, 4, and 5, were successfully characterized by various physicochemical methods including X-ray crystallography. Further reactivity for 3 and 4 will be discussed.
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Characterization and Applications of Coordination Compounds
7:00 PM-10:00 PM, Tuesday, August 21, 2007 BCEC -- Exhibit Hall - B2, Poster
Sci-Mix
Division of Inorganic Chemistry |
