Sulfinyl nitrenes can be generated from the unstable sulfinyl azides (R-SON3). However this reaction easily results in explosions and unpredictable results.[1][2]
Sulfinyl nitrenes can be prepared from a sulfinylhydroxylamine, with R–O–N=S=O, by a reaction with an organometallic M-R1 compound to yield R1SON.[1]
Sulfinyl nitrenes have a resonance structure between sulfur in a +6 oxidation state and a triple bond to nitrogen, or sulfur with a +4 state, nitrogen in +1 state and a single bond, or a positive charge on sulfur and a negative charge on nitrogen with a double bond.[1] The dominant state is the singlet state with charge separation and a double bond.[3]
Sulfinyl nitrenes are unstable and react with themselves to yield sulfonyl nitrenes, disulfides or polymerise to trioxotrithiztriazes.[4]
The reaction with water yields a sulfonylamide (R-SO2NH2.[4]
The reaction of a sulfinyl nitrene with sulfoxides results in a sulfonyl sulfoximde, with the oxygen joining the sulfinyl sulfur and its bond replaced by a double bond to nitrogen.[5]
Sulfinyl nitrenes are distinct from sulfonyl nitrenes which have two oxygen atoms attached to the sulfur atom.[1]
Thiazate[7] or thionylimide ([NSO]−)[8] is an anion that exists as alkali metal salts. They can be formed by a tri-tert-butoxy metal reaction with a trimethylsilyl compound:[9]
KOtBu + Me3SiNSO → K[NSO] + Me3SiOtBu
NaNSO, KNSO, RbNSO, CsNSO, (Me2N)3S+NSO−[10] and tris(dimethylamino)sulfonium [(Me2N)3S][NSO] salts are known.[9]
^ abWu, Zhuang; Li, Dingqing; Li, Hongmin; Zhu, Bifeng; Sun, Hailong; Francisco, Joseph S.; Zeng, Xiaoqing (22 January 2016). "Gas-Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN". Angewandte Chemie. 128 (4): 1529–1532. Bibcode:2016AngCh.128.1529W. doi:10.1002/ange.201510105.
^Wentrup, Curt (3 September 2018). "Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry". Angewandte Chemie International Edition. 57 (36): 11508–11521. doi:10.1002/anie.201804863. PMID29808956. S2CID44089179.
^ abMaricich, Tom J.; Hoffman, Virgil L. (December 1974). "Chemistry of benzenesulfinyl azides. Reactions with sulfoxides". Journal of the American Chemical Society. 96 (25): 7770–7781. doi:10.1021/ja00832a026.
^Maricich, Tom J.; Madhusoodanan, Sunderesan; Kapfer, Craig A. (January 1977). "Convergence of mechanisms between sulfinyl azide and N-alkoxysulfinamide reactions". Tetrahedron Letters. 18 (11): 983–986. doi:10.1016/S0040-4039(01)92808-4.
^Wu, Zhuang; Liu, Qifan; Li, Dingqing; Feng, Ruijuan; Zeng, Xiaoqing (March 2017). "Flash vacuum pyrolysis of methoxysulfinyl azide: Stepwise decomposition via methoxysulfinyl nitrene". Journal of Analytical and Applied Pyrolysis. 124: 610–617. doi:10.1016/j.jaap.2017.01.001.
^Armitage, D. A. (?Fred?); Brand, John C. (1979). "Potassium thiazate KNSO". Journal of the Chemical Society, Chemical Communications (23): 1078. doi:10.1039/C39790001078.
^Mann, S.; Jansen, M. (January 1995). "Zur Kenntnis der Alkalimetallthionylimide". Zeitschrift für anorganische und allgemeine Chemie. 621 (1): 153–158. doi:10.1002/zaac.19956210128.