Iminosulfur Oxydifluoride and Poly-(oxofluorosulfur nitride)

Parshall, G. W.; Cramer, Richard C.; Foster, Rod

doi:10.1021/ic50003a045

Cited by 28 publications

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“…In 1991 we reported that cyclic thionylphosphazenes 1a and 1b undergo thermal ring-opening polymerization (ROP) to yield the poly(thionylphosphazenes) 2 , a new class of inorganic polymers with skeletal four-coordinate sulfur(VI), nitrogen, and phosphorus atoms. , These polymers 9-14 can be regarded as hybrids of poly(oxothiazenes) [RS(O)N] n − and classical polyphosphazenes [R 2 PN] n …”

Section: Introductionmentioning

confidence: 99%

“…[7][8][9][10][11][12][13][14] In 1991 we reported that cyclic thionylphosphazenes 1a and 1b undergo thermal ring-opening polymerization (ROP) to yield the poly(thionylphosphazenes) 2, a new class of inorganic polymers with skeletal four-coordinate sulfur(VI), nitrogen, and phosphorus atoms. 10,11 These polymers [9][10][11][12][13][14] can be regarded as hybrids of poly(oxothiazenes) [RS(O)dN] n [15][16][17] and classical polyphosphazenes [R 2 PdN] n . 6 We have previously described in detail the synthesis and properties of poly(thionylphosphazenes) with aryloxy substituents via the reaction of 2a or 2b with sodium aryloxides Na[OAr].…”

Section: Introductionmentioning

confidence: 99%

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Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Park

Liang

et al. 1996

Macromolecules

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Aminolysis of the halogenated poly(thionylphosphazene) [NSOCl(NPCl2)2]n (2a), which possesses a novel S(VI)-N-P backbone, with a series of primary amines NH2R (R ) Me, Et, n Pr, allyl, n Bu, n Hex, and Ph) afforded the hydrolytically stable poly[(aminoPh) in which both the chlorine substituents at the phosphorus center and at sulfur were replaced. Treatment of 2a with a mixture of amines, NH2R (R ) allyl and n Bu), yielded a series of mixed substituent copolymers 5a-5c of which 5a and 5b were thermally and UV cross-linkable. These new polymers were structurally characterized by 31 P, 1 H, and 13 C NMR and IR spectroscopy and by elemental analysis. The stereochemistry of the poly[(amino)thionylphosphazenes] was investigated by 31 P NMR which indicated the polymers are atactic. Molecular weights of the polymers 4a-4g and 5a-5c were in the range Mw ) 5.0 × 10 3 to 1.3 × 10 5 , Mn ) 3.3 × 10 3 to 7.4 × 10 4 according to GPC analysis in THF versus polystyrene standards. An absolute value of Mw ) 1.0 × 10 5 was obtained by low-angle laser light scattering for 4e, which was approximately double that obtained by GPC (Mw ) 4.9 × 10 4 ). The thermal transition behavior of the polymers was investigated by DSC. Glass transition temperatures (Tg's) of the poly[(amino)thionylphosphazenes] 4a-4g and 5a-5c were in the range of -40 to +82 °C. No melt transitions were detected and wide-angle X-ray scattering studies also indicated that poly[(amino)thionylphosphazenes] were amorphous. TGA analysis showed that the poly[(amino)thionylphosphazenes] were stable to weight loss up to 200-250 °C under nitrogen at a heating rate of 10 °C/min.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Park

Liang

et al. 1996

Macromolecules

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“…H,5NSOF2 was prepared following Parshall's procedure. 2 The reaction is preferably run in diethyl ether and the immediate product is an azeotrope from which H15NSOF2 can be distilled following addition of BF3 to neutralize the ether. However, as our synthesis had to be scaled down (0.38 g of !5NH3 as starting material) careful microdistillation yielded a fraction boiling at maximum 40 °C (about 20% H15NSOF2).…”

Section: Methodsmentioning

confidence: 99%

Microwave spectrum, structure, dipole moment, and quadrupole coupling constants of iminosulfur oxydifluoride

Cassoux¹,

Kuczkowski²,

Creswell³

1977

Inorg. Chem.

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“…The synthesis of HNSOFz has also recently been carried out [66]. During further hydrolysis of HNSOFz another proton is transferred to the nitrogen with the formation of iminosulfur dioxyfluoride, H2NS02F (lo), which can also be obtained synthetically [67,68].…”

Section: Thiazyl Trifluoride Nsf3 [62]mentioning

confidence: 99%

Recent Investigations of Sulfur‐Nitrogen Compounds

Glemser

1963

Angew. Chem. Int. Ed. Engl.

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1.With increasing temperature, transitions occur from a nonmetallic structure of low coordination number to a more metallic structure of higher coordination [IS]. 2. Only in tin does this transition already take place in the solid state; in the other cases, the melting point coincides with the transition point. The entropy of fusion is always large; the volume change on melting is generally negative (Ga, Si, Ge, Bi: or very slightly positive (Sb); the rather large expansion of As and the normal value for Te are exceptional and depend on the fact that the structural transformations occurring there on melting are incomplete.3. The structural changes can be initiated (As) or completed (Sn) by second-order transitions in the solid state. 4. The transitions are not complete on melting; they often continue to a greater or less degree above the melting point (especially for As, but also for Te, and possibly for Sb and Bi) [19].Ordinate: Logarithm of the "atomic" conductivity Abscissa: Temperature [ "Cl the jump in conductivity is large and positive for the first three elements mentioned. In spite of their met a 11' iccontluctivity in the solid state, Bi and Sb are better conductors in the liquid state. For arsenic this holds only at high temperatures, i.e. when the transition to a metallic structure is complete.We wish to thank the Fonds der Chemischen Industrie and the Deutsche ~orschun~~s~emeinschajt for supporting tfiese studies.The preparation, properties, and structure of cyclic and acyclic sulfilr-nitrogen halides arc' discussed. In the cyclic compounds, S -N rings with localized and delocalized n-bonds occur. In acyclic halides, S-N triple bonds are observed. Organic iminosulfur dihalides are discussed.

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Iminosulfur Oxydifluoride and Poly-(oxofluorosulfur nitride)

Cited by 28 publications

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Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones: Synthesis, Characterization, and Properties of Atactic Poly[(amino)thionylphosphazenes]

Microwave spectrum, structure, dipole moment, and quadrupole coupling constants of iminosulfur oxydifluoride

Recent Investigations of Sulfur‐Nitrogen Compounds

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