TAS+(Z)-Me3CNSN- and TAS+(E)-Me3SiNSN-:  Does the Anion−Cation Interaction Influence the Configuration?

Borrmann, Tobias; Zibarev, Andrey V.; Lork, Enno; Knitter, Gerd; Chen, Shan-Jia; Watson, Paul G.; Cutin, Edgardo H.; Шакиров, М. М.; Stohrer, Wolf‐Dieter; Mews, Rüdiger

doi:10.1021/ic0004030

Cited by 17 publications

(19 citation statements)

References 32 publications

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“…[21][22][23][24] For instance, in thiazyl fluorides FStN and F 3 StN the SN bond length, according to the data from microwave spectroscopy, is equal to 1.448 and 1.416 Å, respectively, 21,22 whereas in the thiazylamide anions RsNsStN (RdAr, Alk), according to X-ray diffraction analysis, it ranges from 1.442 to 1.490 Å. 23,24 Note, that the calculated length of heterocyclic SN bond (1.577 Å) is quite typical of a double bond, 1a,25 while the heterocyclic SS bond (2.19 Å) is predicted to be slightly longer than a typical single bond (2.05 ( 0.05 Å). 26 It is evident from Figure 3 (spectrum 3) that secondary 313-nm photolysis leads to a significant growth of the band intensities in the visible region, whereas the UV band grows much less than initially.…”

Section: Resultsmentioning

confidence: 99%

Matrix Isolation and Computational Study of the Photochemistry of 1,3,2,4-Benzodithiadiazine

et al. 2007

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Photolysis of 1,3,2,4-benzodithiadiazine (1) at ambient temperature yields stable 1,2,3-benzodithiazolyl radicals. In order to reveal the mechanism of this unusual transformation, the photochemistry of 1 was studied in argon matrices using IR and UV-vis spectroscopy. A series of intermediates, including four-and fivemembered heterocyclic and o-quinoid acyclic species, were characterized spectroscopically with the help of quantum chemical calculations. With selective irradiation, these intermediates can be mutually interconverted as well as converted back to the starting compound 1.

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Section: Resultsmentioning

confidence: 99%

Matrix Isolation and Computational Study of the Photochemistry of 1,3,2,4-Benzodithiadiazine

et al. 2007

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“…The X-ray structure of salt 2 was not Ϫ anion (salt 3) demonstrates the stereoelectronically unfavorable E-configuration (Figure 4), previously also observed for its TAS ϩ salt (for the in-depth discussion of the Z-and E-configurations and the bonding properties of the [RNSN] Ϫ anions, see refs. [7,8] ). In the salts with the anions in the Z-configuration, the K ϩ counterion (encapsulated in the crown ether) is coordinated only by the terminal nitrogen atom ( Ϫ anion is significantly narrower than in the other [RNSN] Ϫ anions (Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…While the terminal sulfurϪnitrogen bond length falls into the range established for the S IV ϵN triple bond (146Ϫ148 pm), the internal sulfurϪnitrogen bond is 9Ϫ13 pm longer ( Table 2. Selected bond lengths (pm), bond angles (°) and N···K ϩ separation (pm) in salts 1, 3Ϫ6 (for atom numbering see Figure 1Ϫ5); for comparison, the data of the corresponding TAS ϩ salts of 2, [7] 3, [7] and 5 [8] [7] 147. 3(TAS ؉ ) [7] 171.…”

Section: Resultsmentioning

confidence: 99%

“…[7,8] It follows from a preliminary analysis of the calculations at the MP2/6-31ϩG* level of theory that this reorganization is driven to some extent by the reduction of the local symmetry at the S atom. [25,26] 2Ϫ dianion (salt 6) is the genuine aza-analogue of sulfur dioxide OϭSϭO (and isoelectronic with ozone, O 3 ).…”

Section: Same [Rnsn]mentioning

confidence: 99%

“…Our theoretical calculations (Table 3) agree reasonably well with our experimental results. [7,30,31] (nitrogen NMR spectroscopy of binary sulfur-nitrogen anions, see ref.…”

Section: Same [Rnsn]mentioning

confidence: 99%

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Preparation and Structural Characterization of [K(18‐crown‐6)]⁺ Salts of [RNSN]⁻ Anions and the [NSN]²⁻ Dianion

et al. 2004

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Abstract[K(18‐crown‐6)]+ salts of the [RNSN]− anions (R = Alk, Ar) and the [NSN]2− dianion, which are thermally stable and very soluble in aprotic organic solvents, were prepared from [K(18‐crown‐6)]+[tBuO]− and the corresponding R−N=S=N−SiMe3 and (Me3Si−N=)2S, respectively. The salts are characterized by multinuclear (1H, 13C, 14N, 19F, 29Si and 39K) NMR spectroscopy in solution and by X‐ray diffraction in the solid state. The experimentally determined bond lengths confirm that the [RNSN]− anions are thiazylamides, R−N−−S≡N rather than sulfur diimides, R−N=S=N−. Relative to O=S=O, in the [NSN]2− dianion, which is the genuine aza‐analogue of sulfur dioxide, the bond lengths are elongated and the bond angle is widened. This might reflect electrostatic repulsion between the negatively charged N atoms. The experimental results are in agreement with theoretical calculations (RHF, B3LYP, MP2). In the nitrogen NMR spectra, when going from [AlkNSN]− to [ArNSN]−, the low‐field signal of the terminal (unsubstituted) N atom reveals further deshielding, whereas the high‐field signal of the internal (substituted) N atom displays further shielding. The 14N NMR resonance for the [NSN]2− dianion is practically insensitive to the counterion. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Sulfur–Nitrogen Compounds

Chivers

2005

Encyclopedia of Inorganic Chemistry

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The quintessential sulfur–nitrogen compound, tetrasulfur tetranitride, S 4 N 4 , was first detected in 1835, just 10 years after the discovery of benzene. Its unusual structure, like that of benzene, was not elucidated for over 100 years. The application of diffraction techniques revealed the unusual cage arrangement with two weak cross‐ring sulfur–sulfur interactions. The details of the electronic structure of this fascinating molecule are still a matter for debate today. The polymer, (SN) x , was first obtained in 1910 and its metallic character was noted. However, it was the discovery in 1973 that a polymer comprising only nonmetallic elements behaves as a superconductor at 0.26 K that sparked widespread interest in sulfur–nitrogen (SN) chemistry. A year later it was proposed that planar SN heterocycles belong to a class of ‘ electron‐rich aromatics ’ that conform to the well‐known Hückel (4n + 2)π‐electron rule of organic chemistry. This suggestion, which was based on simple electron‐counting concepts, provided an additional impetus for both experimental and theoretical investigations of SN systems. In the past thirty years, the combination of structural studies, primarily through X‐ray crystallography, spectroscopic information, and molecular orbital calculations has provided reasonable rationalizations of the structure–reactivity relationships of these fascinating compounds. Interfaces with other areas of chemistry, for example, materials chemistry, organic synthesis, coordination chemistry, and biochemistry have been established and are under active investigation. For example, in the area of solid‐state chemistry, materials with unique magnetic and conducting properties that depend on intermolecular sulfur–nitrogen interactions between radical species have been designed. These new materials have potential applications in the construction of organic data recording devices. At the other end of the chemical spectrum, S ‐nitrosothiols (RSNO) have been shown to be important species in the storage and transport of nitric oxide. As NO donors, these SN compounds have potential medical applications in the treatment of blood circulation problems. This contribution begins with a short discussion of structure and bonding in cyclic SN species. This is followed by an overview of the various physical methods that are used to characterize SN compounds. The subsequent sections deal with specific classes of SN compounds starting with binary species, which include cations and anions as well as neutral molecules. The next sections are concerned with two important classes of reagents, SN halides and SN oxides. Heterocyclothiazenes, in which a sulfur atom in an SN ring is replaced by another atom, most commonly carbon, phosphorus, or a transition metal, constitute a continually expanding area of investigation as reflected in the relatively large section on this topic. Sulfanuric ring systems, which involve sulfur in the +VI oxidation state, have been known for many years and recent interest has revolved around polymers involving the NS(O)R repeating unit, which are isoelectronic with the well‐known polyphosphazenes. The next section describes the chemistry of cyclic sulfur imides, that are structurally related to the cyclic sulfur allotropes by the replacement of one or more sulfur atoms by an imido (NR) group. In the final sections, the unusual properties of SN chains, including the unique polymer (SN) x are discussed.

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TAS⁺(Z)-Me₃CNSN^- and TAS⁺(E)-Me₃SiNSN^-: Does the Anion−Cation Interaction Influence the Configuration?

Cited by 17 publications

References 32 publications

Matrix Isolation and Computational Study of the Photochemistry of 1,3,2,4-Benzodithiadiazine

Matrix Isolation and Computational Study of the Photochemistry of 1,3,2,4-Benzodithiadiazine

Preparation and Structural Characterization of [K(18‐crown‐6)]⁺ Salts of [RNSN]⁻ Anions and the [NSN]²⁻ Dianion

Sulfur–Nitrogen Compounds

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TAS+(Z)-Me3CNSN- and TAS+(E)-Me3SiNSN-: Does the Anion−Cation Interaction Influence the Configuration?

Cited by 17 publications

References 32 publications

Matrix Isolation and Computational Study of the Photochemistry of 1,3,2,4-Benzodithiadiazine

Matrix Isolation and Computational Study of the Photochemistry of 1,3,2,4-Benzodithiadiazine

Preparation and Structural Characterization of [K(18‐crown‐6)]+ Salts of [RNSN]− Anions and the [NSN]2− Dianion

Sulfur–Nitrogen Compounds

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TAS⁺(Z)-Me₃CNSN^- and TAS⁺(E)-Me₃SiNSN^-: Does the Anion−Cation Interaction Influence the Configuration?

Preparation and Structural Characterization of [K(18‐crown‐6)]⁺ Salts of [RNSN]⁻ Anions and the [NSN]²⁻ Dianion