Sulfur-Nitrogen Compounds with 4-Coordinate Sulfur

Baumann, Norbert; Fachmann, Hans-Jürgen; Heibel, Brigitte; Jotter, Reimund; Ledüc, Birgit; Kubny, Alfons

doi:10.1007/978-3-662-06363-7_2

Cited by 1 publication

(2 citation statements)

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“…Curiously, therefore, while the synthetic value of N -sulfinylamines has been well explored, their hydrolysis, a seemingly straightforward reaction, is not well understood. In particular, the fact that the substituent R has a dramatic effect on the reactivity of compounds R−NSO with water , has not been investigated extensively. While the aliphatic N -sulfinylamines are reported to hydrolyze readily, the aromatic compounds and N -sulfinylhydrazides (R−CO−NH−NSO) are less moisture-sensitive, and N -sulfinylhydrazines (R−NH−NSO) do not react with water …”

Section: Introductionmentioning

confidence: 99%

“…In particular, the fact that the substituent R has a dramatic effect on the reactivity of compounds R−NSO with water , has not been investigated extensively. While the aliphatic N -sulfinylamines are reported to hydrolyze readily, the aromatic compounds and N -sulfinylhydrazides (R−CO−NH−NSO) are less moisture-sensitive, and N -sulfinylhydrazines (R−NH−NSO) do not react with water , Consequently, an understanding of the effect of the substituent on the reactivity of N -sulfinyl species with water is desirable.…”

Section: Introductionmentioning

confidence: 99%

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Hydrolysis ofN-Sulfinylamines and Isocyanates: A Computational Comparison

Ivanova

Muchall

2007

J. Phys. Chem. A

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A comparative study of the concerted hydrolysis of H-, CF3-, CH3-, and Ph-substituted N-sulfinylamines (R-NSO) and isocyanates (R-NCO) was performed using B3LYP/6-31+G(2d,2p). The "two-water-molecule" model was found to be sufficient for a proper description of the hydrolysis reaction for both classes of compounds. Despite their overall similar reactivity, N-sulfinylamines react across both the N=S and the S=O bonds, whereas isocyanates hydrolyze predominantly through the N=C bond, in agreement with the proton affinities of the nitrogen and oxygen atoms. The charges on sulfur (N=S=O) and carbon (N=C=O) were found to correlate well with the activation enthalpy for hydrolysis. While the reactivity of an N-sulfinylamine toward water increases with increasing electron-withdrawing ability of the substituent, the substituent effect on isocyanates becomes notable only in the presence of the strongly electron-withdrawing CF3 group.

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Section: Introductionmentioning

confidence: 99%