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Sulfinyl nitrene

Topic: Chemistry

 From HandWiki - Reading time: 3 min
Generic chemical structure of a sulfinyl nitrene

A sulfinyl nitrene is a chemical compound with generic formula R-S(O)N, with oxygen and nitrogen both bonded to the sulfur atom.

Preparation

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]

Properties

Sulfinyl nitrenes are electrophilic.[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]

Reactions

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]

Examples

Trifluoromethyl sulfinyl nitrene (CF3S(O)N) has been produced as a gas, and isolated in a noble gas matrix.[2]

Methoxysulfinyl nitrene (CH3OS(O)N) was also produced by decomposing the azide.[6]

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]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 Davies, Thomas Q.; Tilby, Michael J.; Ren, Jack; Parker, Nicholas A.; Skolc, David; Hall, Adrian; Duarte, Fernanda; Willis, Michael C. (9 September 2020). "Harnessing Sulfinyl Nitrenes: A Unified One-Pot Synthesis of Sulfoximines and Sulfonimidamides". Journal of the American Chemical Society 142 (36): 15445–15453. doi:10.1021/jacs.0c06986. PMID 32841007. Bibcode: 2020JAChS.14215445D. 
  2. ↑ 2.0 2.1 Wu, 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. doi:10.1002/ange.201510105. Bibcode: 2016AngCh.128.1529W. 
  3. ↑ 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. PMID 29808956. 
  4. ↑ 4.0 4.1 Maricich, 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. Bibcode: 1974JAChS..96.7770M. 
  5. ↑ 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. 
  6. ↑ 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. Bibcode: 2017JAAP..124..610W. 
  7. ↑ Armitage, D. A. (?Fred?); Brand, John C. (1979). "Potassium thiazate KNSO". Journal of the Chemical Society, Chemical Communications (23): 1078. doi:10.1039/C39790001078. 
  8. ↑ 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. 
  9. ↑ 9.0 9.1 Chivers, Tristram; Laitinen, Risto S (2017). "Fundamental chemistry of binary S, N and ternary S, N, O Anions: analogues of sulfur oxides and nitrogen oxido-anions". Chemical Society Reviews 46 (17): 5182–5192. doi:10.1039/C6CS00925E. PMID 28702517. http://jultika.oulu.fi/files/nbnfi-fe202001212900.pdf. Retrieved 2 August 2021. 
  10. ↑ Chivers, Tristram; Schmidt, Kenneth J.; McIntyre, Deane D.; Vogel, Hans J. (1 November 1989). "Spectroscopic studies of N–S–O anions: The reactions of NSO − with elemental sulphur and with S 4 N 4". Canadian Journal of Chemistry 67 (11): 1788–1794. doi:10.1139/v89-277. 



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