ChemInform Abstract: TETRASULFUR PENTANITROGEN FLUORIDE

Isenberg, Wilhelm; Mews, R.; Sheldrick, George M.; Bartetzko, Richard; Gleiter, Rolf

doi:10.1002/chin.198412032

Cited by 2 publications

(2 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Of more importance are the barriers to the interconversions (e.g. 3c + 3a: 27, 47, and 45 kcal/mol for R = C1, F, and NH2, respectively), that for R = F being effectively identical to the barrier recently calculated for inversion at sulphur in S4N,F, 4 (46.7 kcal/mol) (21).…”

Section: Rs(nsnj2sr Isomerssupporting

confidence: 52%

Formation and reactivity of transannular sulphur–sulphur bonds in cyclothiazenes and related compounds. A molecular orbital analysis

Oakley¹

1984

Can. J. Chem.

View full text Add to dashboard Cite

The structural dichotomy exhibited by heterocyclic thiazenes of the type E(NSN)?E (E = CR, SR) is analyzed in the light of MNDO molecular orbital calculations on a variety of model structures. For RS(NSN),SR molecules the activation energies for inversion at sulphur have been estimated, and the formation of exo-endo and exo-exo isomers is discussed in terms of the frontier orbitals involved in the free radical and electrophilic oxidation of transannular S-S bonds.RICHARD T . OAKLEY. Can. J. Chern. 62, 2763Chern. 62, (1984.En se basant sur des calculs d'orbitales moltculaires du type MNDO, effectuCs sur une varittC de structures rnodkles, on a analysC la dichotomie de structure que prtsentent les thiazknes hCttrocycliques du type E(NSN)zE (E = CR, SR). Dans le cas des molCcules RS(NSN)?SR, on a CvaluC les Cnergies d'activation pour I'inversion au niveau du soufre et on discute de la formation des isomkres exo-endo et e.ro-exo en fonction des orbitales frontikres irnpliqukes dans les oxydations radicalaire et Clectrophile des liaisons S-S transannulaires.[Traduit par le journal] Introduction The structural diversity of binary sulphur nitride derivatives has evoked continued debate over the electronic factors which control their shape. The cage-like molecule of S4N4 has attracted the most attention (see, for example, ref. I), and the results of recent structural and theoretical (molecular orbital) studies on the protonated form S4N4H+ have illustrated how the energetic balance between different structural modifications can be shifted by a seemingly minor chemical change (2).In addition to the simple binary molecule, S4N4, a variety of heterocyclic derivatives of the type E(NSN),E have recently been synthesized and structurally characterized (E = CPh, CNMe,, PMe,, PPh,, SCI, SNMe,, SNPPh,) (3-8). The molecular structures of these derivatives fall into two distinct categories exhibiting either an essentially planar shape, e.g. 1, or a puckered conformation with a close (2.50-2.60 A) transannular sulphur-sulphur contact, e.g. 2. Although the reasons

show abstract

Section: Rs(nsnj2sr Isomerssupporting

confidence: 52%

Formation and reactivity of transannular sulphur–sulphur bonds in cyclothiazenes and related compounds. A molecular orbital analysis

Oakley¹

1984

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…but in the AsF; salt no ion pairing is observed (92). Replacement of chlorine by fluorine (93) or imine groups (73b, 94) produces discrete covalent structures.…”

Section: Binary Cutionsmentioning

confidence: 99%

Cyclic and Heterocyclic Thiazenes

Oakley

1988

Progress in Inorganic Chemistry

127

View full text Add to dashboard Cite

Scheme I1A second binary compound, tetrasulfur dinitride (S4N2, 4), was also isolated before the end of the last century (32). Its correct elemental composition, however, was not established until 1925 (33), and its molecular formula not confirmed until 1951 (34). Early estimates suggested the formula N2Sj (32), an observation that attests to the tendency of the molecule to disproportionate above its melting point of 22.5"C (hence, the high sulfur content). The six-membered ring structure with a half-chair conformation was finally confirmed in 1981 (35,36). Most early preparative methods involved a thermal decomposition, for example, of S4N, in the presence of sulfur and/or carbon disulfide (37,38). More recently the use of simple metathetical reactions, for example, between Ni(S2N2H)? and S2CI2 has been explored (39). A simple procedure involving the reaction of aqueous ammonia with sulfur monochloride has also been developed (40); although the yield is low (<2%), the method provides a convenient preparation of small quantities (<0.5 g) starting from commercially available materials (3%). The solid state polymerization of S4N2 to (SN), ( 5 ) has recently been reported (36); this process is presumably initiated by trace amounts of (radical) impurities since, when recrystallized from diethyl ether, solid S,N, is indefinitely stable below its melting point (3%).Disulfur dinitride (6) (Scheme 11) was first generated (inadvertently) by Burt in 1910 (41) during an attempt to remove sulfur impurities from SJNJ by passing a vaporous mixture of the two over finely divided silver. At the time he noted the formation of a blue film [later characterized as (SN), polymer]. This reaction has been studied extensively since then, and now 304 RICHARD T. OAKLEY

show abstract

ChemInform Abstract: TETRASULFUR PENTANITROGEN FLUORIDE

Abstract: Die in flüssigem SO2 durch F‐‐Addition (A) dargestellte Titelverbindung (I) wird durch Einengen der SO2‐Lösung in Form farbloser Einkristalle abgeschieden (rasche Dunkelfärbung durch Hydrolyse bzw. Zersetzung).

Cited by 2 publications

References 1 publication

Formation and reactivity of transannular sulphur–sulphur bonds in cyclothiazenes and related compounds. A molecular orbital analysis

Formation and reactivity of transannular sulphur–sulphur bonds in cyclothiazenes and related compounds. A molecular orbital analysis

Cyclic and Heterocyclic Thiazenes

Contact Info

Product

Resources

About