POLY(ALKYL/ARYLOXOTHIAZENES), [N=S(O)R](N) - NEW DIRECTION IN INORGANIC POLYMERS

The thermally-induced condensation polymerization of appropriately substituted N-silylsulfonimidates and free sulfonimidates affords the new sulfur(VI)-nitrogen backbone inorganic polymers, poly(alkyl/aryloxothiazenes), [N=S(O)R](n). A novel synthetic approach, involving a facile restructuring of sulfonamides without affecting the oxidation state of sulfur, was utilized in the preparation of the polymer precursor N-trimethylsilylsulfonimidates, Me(3)SN=S(O)R(1)(OR(2)). These N-silylated sulfonimidates readily undergo desilylation with methanol to yield free sulfonimidates, HN=S(O)R(1)(OR(2)). In some respects, the free sulfonimidates appear to be superior ''monomers'' for the synthesis of the title polymers. Both homopolymers and copolymers are accessible from the condensation polymerization. The first examples of this new class of polymers have been characterized by GPC, DSC, TGA, NMR, and elemental microanalysis. Theoretical calculations have also been performed on poly(methyloxothiazene), [N=S(O)CH3](n).