Sulfinyl nitrene

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Generic chemical structure of a sulfinyl nitrene Sulfinyl nitrene.svg
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.

Contents

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 2 3 4 5 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. Bibcode:2020JAChS.14215445D. doi:10.1021/jacs.0c06986. PMC   7498162 . PMID   32841007.
  2. 1 2 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. Bibcode:2016AngCh.128.1529W. doi:10.1002/ange.201510105.
  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. S2CID   44089179.
  4. 1 2 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. Bibcode:1974JAChS..96.7770M. doi:10.1021/ja00832a026.
  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. Bibcode:2017JAAP..124..610W. doi:10.1016/j.jaap.2017.01.001.
  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. 1 2 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" (PDF). Chemical Society Reviews. 46 (17): 5182–5192. doi:10.1039/C6CS00925E. PMID   28702517 . 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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