Refinement of the structure of N-phenyl-N'-sulfinylhydrazine, C6H6N2OS, at 120(1) K with neutron data

Sulfur monoxide thermal release from an anthracene-based precursor, spectroscopic identification, and transfer reactivity

“…The metrical data of the NNSO chain of 1 in the solid state ( Fig. 2) compare well with the reported structures of sulfinyl hydrazines (35)(36)(37). One bridgehead proton of the azanorbornadiene scaffold weakly interacts with the terminal oxygen atom, leading to a synperiplanar NNSO arrangement as observed for i Pr2N2SO (36).…”

From Inert to Explosive, The Hydrolytic Reactivity of R−NSO Compounds Understood: A Computational Study

“…Formation of hydrogen-bonded dimers in condensed phases is one of the remarkable features of these species. For N-phenyl-N′-sulfinylhydrazine (Ph−NH−NSO, PhSHn ), two distinct networks of hydrogen bonds have been proposed, one based on experimental X-ray and neutron diffraction studies, , the other on quantum chemical calculations. , While the former work suggests N−H···O interactions only, the latter suggests the participation of intermolecular C o −H o ···O interactions (Figure ), similar to the intramolecular C o −H o ···O in PhSAn (Figure ), which have since been confirmed through 1 H NMR studies . Depending on the solvent, the dimers dissociate upon dilution to varying degrees and monomers would dominate in conditions suitable for hydrolysis studies, yet hydrolysis was not observed experimentally…”

“…Even though more than 600 N-sulfinyl compounds are known, only a few aromatic N-sulfinylamines, ,,− -hydrazines, , and N-sulfinyl mono- (R−S−NSO) and di- (R−S−S−NSO) sulfides − were structurally characterized and their reactivity analyzed to some extent. While it appears that steric hindrance leads to kinetic stabilization, attempts to determine electronic effects of aromatic substitution were not always conclusive due to the presence of multiple substituents. − Quantitatively, the introduction of a methyl group in para -position of N-sulfinylaniline caused a decrease in the rate constant of its hydrolysis, with the induction period increasing from 4 to 10 h, suggesting that electron-donating substituents stabilize N-sulfinylamines toward water.…”