Structural characteristics of dithiolene and nitronyl nitroxide salts: a unique oxygenation?deoxygenation process
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Neil Robertson, Simon Parsons, Kunio Awaga and Wataru Fujita
Abstract
Slow interdiffusion of acetonitrile solutions of [TBA][Ni(bdt)2] (bdt = 1,2-denzenedithiol) and [MPYNN][I] (MPYNN = 4,4,5,5-tetramethyl-2-(1-methyl-4-pyridinio)-3-oxide-4,5-dihydro-1H-1-imidazolyloxyl) resulted in two sets of crystals suitable for X-ray analysis. One of these showed a 2 : 1 salt comprising 1-methyl-4(1H-4,5-dihydro-4,4,5,5-tetramethylimidazol-2-yl)pyridinium, resulting from double deoxygenation of [MPYNN]+, and [Ni(bdt)2]? with two oxygen atoms bonded to two of the sulfur atoms in a trans configuration suggesting an oxygen-transfer reaction between the two components. The salt packed with mixed stacks of anions and cations. The second structure showed the starting complex [TBA][Ni(bdt)2], only the second structural characterisation of the radical [Ni(bdt)2]?. Strong interactions between the complexes are prevented by alkyl arms of the countercation