%0 Journal Article %1 citeulike:894053 %A Roy, Aroop K. %A Burns, Gary T. %A Lie, George C. %A Grigoras, Stelian %D 1993 %J J. Am. Chem. Soc. %K chiral-sulfur %N 7 %P 2604--2612 %T Poly(alkyl/aryloxothiazenes): inorganic polymers with a sulfur(VI)-nitrogen backbone. Synthesis, characterization, and theoretical calculations %V 115 %X N-Silylsulfonimidates Me3SiN=S(0)(RI)OR2, 3 with appropriate R2 groups have been found to undergo thermally induced condensation to produce the sulfur(V1)-nitrogen backbone polymers poly(alky1- or aryloxothiazenes), N=S(0)R1, 4 and 5. Polymers 4 and 5 represent the first alkyloxothiazene polymers and the first characterized aryloxothiazene polymers. Modeled after the well-known condensation of N-silylphosphoranimines to poly(phosphazenes), the polycondensation of 3 to 4 appears to be a fairly general reaction. The design and novel synthesis of 3 are described in a companion article. The thermal condensation of 3 is catalyzed by Lewis acids and bases such as BF3-Et20, AlC13, fluoride ion, and phenoxide ion. Additionally, 3 can be quantitatively desilylated with methanol (without side reactions) to the "free" sulfonimidates HN=S(0)(R1)OR2, 71. The free sulfonimidates, in turn,condenserapidly andquantitatively (at rates approximately two orders of magnitude faster and at temperatures 20 to 40 O C lower, than 3) to poly- (oxothiazenes). The polymers have been characterized by gel permeation chromatography, NMR spectroscopy, thermoanalytical methods, and by elemental microanalysis. Theoretical calculations indicate a cis-trans helical conformation for poly(methy1oxothiazene) 4a to be the most stable conformation. A major difference with phosphazene structure geometry is indicated by a near-tetrahedral N S - N bond angle of 103O.

@article{citeulike:894053, abstract = {N-Silylsulfonimidates [Me3SiN=S(0)(RI)OR2, 3] with appropriate R2 groups have been found to undergo thermally induced condensation to produce the sulfur(V1)-nitrogen backbone polymers poly(alky1- or aryloxothiazenes), [N=S(0)R1], 4 and 5. Polymers 4 and 5 represent the first alkyloxothiazene polymers and the first characterized aryloxothiazene polymers. Modeled after the well-known condensation of N-silylphosphoranimines to poly(phosphazenes), the polycondensation of 3 to 4 appears to be a fairly general reaction. The design and novel synthesis of 3 are described in a companion article. The thermal condensation of 3 is catalyzed by Lewis acids and bases such as BF3-Et20, AlC13, fluoride ion, and phenoxide ion. Additionally, 3 can be quantitatively desilylated with methanol (without side reactions) to the "free" sulfonimidates [HN=S(0)(R1)OR2, 71. The free sulfonimidates, in turn,condenserapidly andquantitatively (at rates approximately two orders of magnitude faster and at temperatures 20 to 40 O C lower, than 3) to poly- (oxothiazenes). The polymers have been characterized by gel permeation chromatography, NMR spectroscopy, thermoanalytical methods, and by elemental microanalysis. Theoretical calculations indicate a cis-trans helical conformation for poly(methy1oxothiazene) 4a to be the most stable conformation. A major difference with phosphazene structure geometry is indicated by a near-tetrahedral N S - N bond angle of 103O.}, added-at = {2006-10-23T11:08:30.000+0200}, author = {Roy, Aroop K. and Burns, Gary T. and Lie, George C. and Grigoras, Stelian}, biburl = {https://www.bibsonomy.org/bibtex/21fab5a1dc46c4391614ec3ab73ced932/robert}, citeulike-article-id = {894053}, interhash = {417045f9e140b1d13df64d5b4f0eb04f}, intrahash = {1fab5a1dc46c4391614ec3ab73ced932}, journal = {J. Am. Chem. Soc.}, keywords = {chiral-sulfur}, number = 7, pages = {2604--2612}, priority = {2}, timestamp = {2006-10-23T11:08:30.000+0200}, title = {Poly(alkyl/aryloxothiazenes): inorganic polymers with a sulfur(VI)-nitrogen backbone. Synthesis, characterization, and theoretical calculations}, volume = 115, year = 1993 }