A Singlet Thiophosphoryl Nitrene and Its Interconversion with Thiazyl and Thionitroso Isomers

Abstract

Thiophosphoryl nitrenes, R2P(S)N, are thiazirine-like intermediates that have been chemically inferred from trapping products in early solution studies. In this work, photolysis of the simplest thiophosphoryl azide, F2P(S)N3, in solid noble-gas matrices enabled a first-time spectroscopic (IR and UV-vis) identification of the thiophosphoryl nitrene F2P(S)N in its singlet ground state. Upon visible-light irradiation (≥495 nm), it converts into the thionitroso isomer F2P-N═S, which can also be produced in the gas phase from flash vacuum pyrolysis of F2P(S)N3. Further irradiation of F2P-NS with 365 nm UV light leads to the reformation of F2P(S)N and isomerization to the thiazyl species F2P-S≡N.

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry

“…At hiophosphoryl nitrene F 2 P(S)N was obtained in its singlet ground state by photolysis of the azide.Onirradiation with visible light it rearranged to the thionitroso isomer F 2 PÀ N = S, which was also produced by FVP.Further irradiation at 365 nm caused re-formation of F 2 P(S)N as well as isomerization to the thiazyl F 2 P À S N. [44] Fluorosulfonyl nitrene FSO 2 Ni ni ts triplet ground state was produced by FVP of FSO 2 N 3 [Eq. (10)],i solated in an Ar matrix, and characterized by IR, UV/Vis,a nd ESR spectroscopy (j D/hc j= 1.620; j E/hc j= 0.0055 cm À1 ).…”

“…On irradiation with visible light it rearranged to the thionitroso isomer F 2 P−N=S, which was also produced by FVP. Further irradiation at 365 nm caused re‐formation of F 2 P(S)N as well as isomerization to the thiazyl F 2 P−S≡N …”

Gas‐Phase Generation and Decomposition of a Sulfinylnitrene into the Iminyl Radical OSN

“…[1,2] Singlet nitrenes can be rendered more stable by electron donation to the electron-deficient nitrene center. Thed onation may come from the lone pair of the geminal atom such as oxygen (in a-oxo nitrenes RC(O)N, [3] R 2 P(O)N, [4] and RS-(O) 2 N [5] )a nd sulfur (in the heavier analogues RC(S)N [6] and R 2 P(S)N [7] ). Another type of effective stabilizing interaction is the delocalization of the lone pair from the atom which is directly bonded to the nitrene center, such as in aminonitrene (R 2 N-N), [8] sulfenylnitrene (RS-N), [9] and phosphinonitrene (R 2 P-N).…”

Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase

“…Upon an ArF excimer laser (193 nm) irradiation, decomposition of F 2 P(S)NCO occurs as evidenced by the depletion of its IR band (Figure 4, lower trace). As a result, the IR bands for CO (e, 2140.2 cm À 1 ), [33] F 2 P(S)N (b, 1184.2, 927.1 and 872.4 cm À 1 ) and F 2 PNS (c, 1223.2, 841.2 and 823.9 cm À 1 ) [34] appear. Additionally, a new species displaying a distinguishable IR band at 2271.7 cm À 1 (f) also forms, and it coincides with the strongest IR band for F 2 PNCO (2271 cm À 1 , Ar-matrix).…”