Darstellung, Charakterisierung, quantenchemische Berechnungen und chemische Reaktionen von Schwefeldiimin, dessen Ag- und Tl-Salze sowie TlNSO

The first stable RNSNH sulfur diimide

“…are well-known reagents and ligands. However, the parent compound H-N=S=N-H is only spectroscopically detected 1,2 under special conditions due to its enormous instability. Seemingly for the same reason, monosubstituted R-N=S=N-H derivatives have neither been isolated nor unambiguously characterised.…”

Isolierung labiler NSO‐Pseudohalogen‐Spezies

“…Flüssige H‐NSO hingegen polymerisiert äußerst schnell zum braunen festen Polythionylimid (HNSO) X . Eine Vielzahl theoretischer Untersuchungen und experimenteller Mikrowellen‐Studien deutete auf eine im Grundzustand planare cis ‐H‐NSO‐Spezies hin (Schema ) . Diese Struktur lässt sich auch vom C 2 v ‐symmetrischen SO 2 ableiten, indem ein Sauerstoffatom gegen eine bivalente Imid‐Gruppe (=NH) ausgetauscht wird.…”

A theoretical investigation of electronic ground state of parent sulfur diimide

“…Experimental studies [4,5] suggest that EZ and ZZ conformers are close in energy and both are more stable than EE in gas phase as well as in dense phase. Table 3 summarizes total and relative electronic energies for structures optimized at various levels.…”

“…In that year Haas et al presented the first reproducible and firm experimental data about presence of PSD in dense phase [5]. Details of their experimental procedure may be found in their paper but the main procedure relied on IR spectra of matrix-isolated species.…”

“…The first detection of PSD in 1985 using gas phase microwave spectroscopy [4] provides direct experimental indications for two of these conformers (EZ and ZZ). Using solid-matrix IR spectroscopy, new evidences have been offered about PSD presence as intermediate reagent in dense phase reactions in 1999 [5].…”