Configurations of 1,3-bis(aryl)-1,3-diaza-2-thiaallenes in the crystal state

Bagryanskaya, I. Yu.; Gatilov, Yuri V.; Zibarev, Andrey V.

doi:10.1070/mc1999v009n04abeh001140

Cited by 9 publications

(2 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is a rare configuration, only otherwise observed in bis (2,4,6‐ tri ‐ tert ‐butylphenyl)sulfurdiimide (CSD refcode: BEQHEK), [35] which also contains very bulky ortho substituents. Aside from these two cases, every example from the CSD of aryl SDIs with at least one ortho substituent crystallize as Z/Z, as does 8 [13b,33, 35–36] . Interestingly, the SC‐XRD of 10 [37] (CSD refcode: HOVYAS01) and 11 [38] (YEFJUO) are found as E/Z.…”

Section: Resultsmentioning

confidence: 99%

“…While 9 crystallizes as E/Z, both phenyl rings are almost orthogonal, torsions of 85.9(3)° and 85.4(3)°, relative to the NSN moiety, presumably due to steric pressure from the large ortho ‐bromine substituents. This is a rare configuration, only otherwise observed in bis (2,4,6‐ tri ‐ tert ‐butylphenyl)sulfurdiimide (CSD refcode: BEQHEK), [35] which also contains very bulky ortho substituents. Aside from these two cases, every example from the CSD of aryl SDIs with at least one ortho substituent crystallize as Z/Z, as does 8 [13b,33, 35–36] .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

Hill,

Boeré

2024

Chemistry A European J

View full text Add to dashboard Cite

The synthesis and extensive characterization of nine aryl sulfur diimides (SDIs, Ar‐NSN‐Ar) are presented with a robust computational and experimental investigation of the fundamental properties of these important members of the thiazyl family of compounds, with particular attention paid to their highly tunable electrochemical behaviour. This is the first work to undertake a systematic comparison of the electrochemical profiles of a coherent series of SDIs to demonstrate and quantify the response of their reduction potentials to substituent electron‐donating and ‐withdrawing properties. This effect is found to be not only exceptionally strong, but also correlates very closely with computed orbital energies. Electron paramagnetic resonance spectroscopy is used to determine the nature, localization, and qualitative lifetimes of the radical anions of SDIs. This work also addresses significant misconceptions about physical properties of SDIs. Experimental data and modern computational methods are employed to provide a resolute answer to the long‐standing contention of the solution‐state conformations of SDIs, and to correct historical mistakes in the assignment of infrared spectroscopic data. High‐quality crystal structures of all SDIs in this work showcase the utility of the recently introduced structural refinement software NoSpherA2, enabling full anisotropic refinement of H‐atoms with accurate C‐H bond lengths.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

Hill,

Boeré

2024

Chemistry A European J

View full text Add to dashboard Cite

show abstract

Reactions of Arylthiazylamides with Internal and External Fluoro Electrophiles − Formation of Products with Unusual Structures

Lork

Mews

Шакиров

et al. 2001

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

The heteroatom reactivity of the title anions [as (Me 2 N) 3 S + and Cs + salts] toward both internal and external fluoro electrophiles has been investigated. The intramolecular nucleophilic cyclization of [ArNSN] − (as the cesium salts) bearing at least one ortho fluorine afforded 2,1,3-benzothiadiazoles (e. g. 2a,b), whereas intermolecular condensation with polyfluorinated pyridine and naphthalene afforded Ar−N=S=N−R with R = 4-Py F (4) and R = 2-Np F (8). Further interaction of [ArNSN] − with 4 or 8 proceeded with the transfer of NSN units resulting in (ArN=) 2 S (5) and [RNSN] − , followed by de-

show abstract

Does a Stabilising Interaction Favouring theZ,ZConfiguration of S‐NSN‐S Systems Exist?

Tersago

Mandado

Alsenoy

et al. 2005

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The existence of the orbital interaction presented in the literature as being the cause for the stabilisation of the Z,Z configuration of Ph-S-N=S=N-S-Ph (1) and its derivatives in the crystal phase, has been investigated. The results of theoretical calculations at the DFT/B3LYP/6-311+G* level of theory suggest that such a stabilising interaction might not exist or be extremely weak and that packing forces must be the main cause of the observed Z,Z configuration in the solid. To reach this conclusion structural and energetic parameters were combined to study the bonding in these -S-N=S=N-S- systems. For the analogous Ph-Se-N=S=N-Se-Ph (2) in particular the isomeric equilibrium in solution found in the variable-temperature 77Se NMR spectrum indicates that, in the gas phase or in solution, the observed Z,Z configuration is not stabilised to a greater extent than the Z,E configuration.

show abstract

Configurations of 1,3-bis(aryl)-1,3-diaza-2-thiaallenes in the crystal state

Cited by 9 publications

References 10 publications

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

Reactions of Arylthiazylamides with Internal and External Fluoro Electrophiles − Formation of Products with Unusual Structures

Does a Stabilising Interaction Favouring theZ,ZConfiguration of S‐NSN‐S Systems Exist?

Contact Info

Product

Resources

About