Ultrafast Spectroscopy and Computational Study of the Photochemistry of Diphenylphosphoryl Azide: Direct Spectroscopic Observation of a Singlet Phosphorylnitrene

Vyas, J. Shubham; Muthukrishnan, Sivaramakrishnan; Kubicki, Jacek; McCulla, Ryan D.; Burdziński, Gotard; Sliwa, Michel; Platz, Matthew S.; Hadad, Christopher M.

doi:10.1021/ja909327z

Cited by 28 publications

(17 citation statements)

References 61 publications

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“…A singlet phosphoryl nitrene intermediate (Ph 2 P(O)N) has been very recently detected by ultra-fast spectroscopy, 43 and its life-time has been estimated to be about 480 ps. Given the low I to II conversion barriers, and the expected rapid singlet-triplet intersystem crossing (ISC) in solid Ar matrices aided by the small DE ST (Table 2), the detection of the most stable triplet nitrene conformer in a solid argon matrix is reasonable.…”

Section: Conformers Of Fp(o)(n 3 )Nmentioning

confidence: 99%

Decomposition of fluorophosphoryl diazide: a joint experimental and theoretical study

Zhu

et al. 2015

Phys. Chem. Chem. Phys.

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Section: Conformers Of Fp(o)(n 3 )Nmentioning

confidence: 99%

Decomposition of fluorophosphoryl diazide: a joint experimental and theoretical study

Zhu

et al. 2015

Phys. Chem. Chem. Phys.

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“…29,34 Phosphoryl azide R 2 P(O)N 3 has been considered to be a potentially useful photoaffinity label in biochemistry, and the photochemistry of diaryl-and dialkylphosphoryl azides in solution has been well investigated. [35][36][37][38][39][40][41] In all cases, complex photolysis products including derivatives of phosphoryl nitrenes in both singlet and triplet states were obtained.…”

Section: Introductionmentioning

confidence: 98%

Conformational composition, molecular structure and decomposition of difluorophosphoryl azide in the gas phase

Zhu

et al. 2015

Phys. Chem. Chem. Phys.

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The conformational composition, molecular structure and decomposition of difluorophosphoryl azide F2P(O)N3 in the gas phase were studied using gas electron diffraction (GED), matrix isolation IR spectroscopy, and quantum-chemical calculations, respectively. While computational methods predict only minor differences in the total energy between the two possible conformers (syn and anti), the analysis of electron diffraction data reveals the dominating abundance of the syn conformer in the gas phase at room temperature. Ab initio frequency analyses suggest that a low-frequency large-amplitude motion of the N3 group with respect to the P-N-N-N torsion is to be expected for the syn conformer. The large amplitude motion was included explicitly into the GED structure refinement procedure. It presumably contributes to a thermodynamic stabilization of the syn-conformer with respect to the anti-conformer in the gas phase at ambient temperature. Upon flash vacuum pyrolysis, this syn conformer undergoes a stepwise decomposition via the difluorophosphoryl nitrene, F2P(O)N, which features as the first experimentally observed phosphoryl nitrene that can be thermally produced in the gas phase. To reveal the reaction mechanism, quantum-chemical calculations on the potential energy surface (PES) of F2P(O)N3 were performed. Both B3LYP/6-311+G(3df) and CBS-QB3 calculation results strongly support a stepwise decomposition into the singlet F2P(O)N, which prefers intersystem crossing to the thermally persistent triplet ground state instead of a Curtius rearrangement into FP(O)NF.

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“…[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).…”

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confidence: 99%

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

et al. 2015

Angew Chem Int Ed

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The dipolar oxathiazyne-like sulfinylnitrene RS(O)N, a highly reactive α-oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF3S(O)N3 at 350 °C, an elusive sulfinylnitrene CF3S(O)N was generated in the gas phase in its singlet ground state and was characterized by matrix-isolation IR spectroscopy. Further fragmentation of CF3S(O)N at 600 °C produced CF3 and a novel iminyl radical OSN, an SO2 analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF3S(O)N3.

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Ultrafast Spectroscopy and Computational Study of the Photochemistry of Diphenylphosphoryl Azide: Direct Spectroscopic Observation of a Singlet Phosphorylnitrene

Cited by 28 publications

References 61 publications

Decomposition of fluorophosphoryl diazide: a joint experimental and theoretical study

Decomposition of fluorophosphoryl diazide: a joint experimental and theoretical study

Conformational composition, molecular structure and decomposition of difluorophosphoryl azide in the gas phase

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

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