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The filled and empty level structures of the thiazyl chains R−NSN−R and (R−NSN)2S, with R = Si(CH3)3, are investigated by means of ultraviolet photoelectron and electron transmission spectroscopy. The spectral features are interpreted with the support of ab initio Hartree−Fock (HF)/6-31G* and semiempirical AM1 calculations, within the Koopmans' theorem approximation, and with density functional theory, using the orbital energies of the transition state electronic configuration. Post-HF calculations with infinite-order coupled-cluster expansion are employed to evaluate the first vertical electron affinity value of R−NSN−R, with R = H and CH3. The experimental and theoretical results obtained for the thiazyl chains, as well as those for trans-oligoethenes, are extrapolated in order to evaluate the first ionization energy and electron affinity values for the corresponding (ideal) gas-phase polymers. Poly(sulfur nitride) is predicted to possess a smaller ionization energy and a sizeably higher electron affinity than those of trans-polyacetylene, with a consequent greatly reduced highest occupied molecular orbital−lowest unoccupied molecular orbital energy gap, in agreement with its highly conductive nature.

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The aromatic, aliphatic or vinylic nitriles (II), (IV) or (VI), on treatment with various aluminum hydrides, afford alumino imine complexes, which give the corresponding silyl imines on subsequent treatment with Me3SiCl.