Derivatives of Cyclic Inorganic Sulfur Imides

Abstract

1) Cyclic inorganic sulfur imides, S₇NH, S₆(NH)₂ 1.3 S₅(NH)₃1.3.5 and S₄(NH)₄1.3.5.7. in solution in polar solvents (acetone, acetonitrile, etc.) release the radicals S₇N-, S₆N₂ ^2- and S₅N^3- under the action of alkali. Their study by near UV spectroscopy reveals unstable radicals which rapidly pass into the more stable S₄N^- radical. The latter in turn gives, by charge transfer with the solvent (acetone), the blue complex [S₄N–OC(CH₃)₂]. Non polar solvents (CCl₄) do not give this charge transfer complex (C.T.C.).

2) The sulfur imides mentioned above react with a solution of S₈ to give, via hydrogen bonds, crystalline C.T.C's of formula [3 S₈–S₇NH.] or [2 S₈–S₆(NH)₂1.3]. X-ray examination reveals that these complexes are isotypes of the sulfurs S₈β and S ₈γ whose crystals are stabilized by intermolecular hydrogen bonds.

3) The reaction of the sulfur imides with formic aldehyde gives primary cyclic polyalcohols, such as S₅(N-CH₂OH)₃ or S₄(N-CH₂OH)₄, which form typical molecular cages through intramolecular hydrogen bonds.

4) Examination of Van der Waals bonds of the crystallized sulfur imides enables their comparison with molecules of these compounds containing other types of bonds.