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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 18, Number 9
BKCSDE 18(9)
September 20, 1997 

 
Title
Synthesis and Characterization of Bis(5,6-dihydro-1,4-dithiin-2,3-dithiolato)nickel(Ⅱ), nickel(Ⅲ) and of Related Dialkyl Nickel(Ⅱ) Dithiolene Complexes
Author
Young-Jin Kim, Sung-Nak Choi*, Yung-Hee Oh Kim
Keywords
Abstract
The reaction between Ni(Ⅱ) and sodium salt of 5,6-dihydro-1,4-dithiin-2,3-dithiolate (DDDT2-) in the presence of oxygen results in the formation of Ni(Ⅲ) species, Ni(DDDT)2-, which is isolated as tetraalkylammonium salt. The same reaction performed in the absence of oxygen yields dianionic Ni(Ⅱ) species, Ni(DDDT)22-, which is also isolated as the tetraethylammonium salt. The bis(5,6-dihydro-1,4-dithiin-2,3-dithiolato) nickelate (Ⅱ) dianion, Ni(DDDT)22-, reacts with methyl iodide to yield unusually stable bis(methylthio)dithiolene complex, Ni(CH3)2C8H8S8. All the isolated dithiolato-nickel(Ⅱ) and nickel(Ⅲ) complexes are characterized by 1H NMR, UV/Vis, IR and mass spectroscopic methods. The internal redox reaction of the nickel(Ⅱ )-dithiolate has been studied by spectro-electrochemical method and the results were compared with those of other metal-dithiolenes. The alkylated nickel(dithiolene) complex presumably undergoes cis-trans isomerization reaction in solution, judging from the experimental results of variable-temperature 1H NMR measurements.
Page
1022 - 1028
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