Photochemistry of phosphenic chloride (ClPO<sub>2</sub>): isomerization with chlorine metaphosphite (ClOPO) and reduction by carbon monoxide

Jiang, Junjie; Zhu, Bifeng; Jiang, Xin; Lü, Bo; Zeng, Xiaoqing

doi:10.1039/d2cp02986c

Cited by 3 publications

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References 80 publications

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“…The IR spectrum for the 266 nm laser photolysis of CH 2 PCl (Figure A) shows the dominant formation of HCP···HCl, which is strongly perturbed by interactions with the surrounding matrix material (CO) as evident by the shifted positions (Table S1) and the doublet splittings for the IR bands of the complex. Only traces of HCO· (1880.0 cm –1 ) and ClCO· (1859.9 cm –1 ) form from the CO-trapping reactions with the photolytically generated H and Cl atoms during the photolysis. Therefore, it is likely that the formation of HCP···HCl from the photodecomposition of CH 2 PCl mainly proceeds via a concerted mechanism of HCl-elimination.…”

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Hydrogen-Bonded π Complexes between Phosphaethyne and Hydrogen Chloride

Jiang

Lü

Zhu

et al. 2023

J. Phys. Chem. Lett.

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The highly labile complexes between phosphaethyne (HCP) and hydrogen chloride (HCl) with 1:1 and 1:2 stoichiometries have been generated in Ar and N 2 matrices at 10 K through laser photolysis of the molecular precursors 1-chlorophosphaethene (CH 2 PCl) and dichloromethylphosphine (CH 3 PCl 2 ), respectively. The IR spectrum of the 1:1 complex suggests the preference of a single "T-shaped" structure in which HCl acts as the hydrogen donor that interacts with the electron-rich C�P triple bond. In contrast, three isomeric structures for the 1:2 complex bearing a core structure of the "T-shaped" 1:1 complex are present in the matrix. The spectroscopic identification of these rare HCP πelectron complexes is supported by D-isotope labeling and the quantum chemical calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level of theory.

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confidence: 99%

Hydrogen-Bonded π Complexes between Phosphaethyne and Hydrogen Chloride

Jiang

Lü

Zhu

et al. 2023

J. Phys. Chem. Lett.

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Light induced reactions in cryogenic matrices (highlights 2021–2022)

Fausto,

Nikitin,

Nogueira

2023

Photochemistry

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This chapter surveys research on light induced reactions of organic molecules investigated in cryogenic matrices that has been reported during 2021 and 2022. It highlights studies dealing with conformational changes, tautomerizations and other structural isomerizations induced either by ultraviolet/visible or infrared light, as well as photofragmentation reactions. Emphasis is given to reactive intermediates, including nitrenes, carbenes and radicals. The studies featured in the present review are examples of recent applications of the matrix isolation method, coupled with spectroscopic probing, to these areas of investigation.

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Spectroscopic Identification and Photochemistry of Astrochemically Relevant Phosphorus-bearing Molecules [O, C, N, P] and [2O, C, N, P]

Zhu,

Wang,

Jiang

et al. 2024

ApJ

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Diatomic molecules phosphorus monoxide (PO) and phosphorus mononitride (PN) are the main reservoirs of gas-phase phosphorus in interstellar and circumstellar environments, indicating the possibility of forming new phosphorus-bearing molecules through reactions with other interstellar species. To explore the astrochemistry of PO and PN, new simple phosphorus-bearing molecules [O, C, N, P] and [2O, C, N, P] were generated in the gas phase and isolated in cryogenic matrices for characterization with matrix-isolation IR and UV/vis spectroscopy in combination with calculations at the CCSD(T)-F12a/VTZ-F12 level of theory. In an inert argon matrix, OPCN isomerizes to OPNC upon UV-light irradiation at 365 nm, followed by successive isomerizations to PNCO and POCN with concomitant dissociation to diatomic PN and CO under further irradiation at 193 nm. By analogy, the isomerization of O2PCN to O2PNC and OPNCO followed by fragmentation to OPN/CO and PN/CO2 occurs in the matrix upon irradiation at 193 nm. In a chemically active CO ice, the photolytic reaction of OPCN with CO yields CO2 and PCN, and O2PCN reacts with CO by forming OPCN and CO2, in which the photochemical networks for these P-bearing species linking the astrochemically important PN and PO have been proposed. The experimental identification of these phosphorus-bearing molecules is supported by quantum chemical calculations, and the spectroscopic data may aid in their detection in the interstellar and circumstellar medium.

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Photochemistry of phosphenic chloride (ClPO₂): isomerization with chlorine metaphosphite (ClOPO) and reduction by carbon monoxide

Abstract: Phosphenic chloride (ClPO2) is an elusive congener of nitryl chloride (ClNO2). By high-vacuum flash pyrolysis of 2-chloro-1,3,2-dioxaphospholane in the gas phase, ClPO2 has been efficiently generated and subsequently isolated in...

Cited by 3 publications

References 80 publications

Hydrogen-Bonded π Complexes between Phosphaethyne and Hydrogen Chloride

Hydrogen-Bonded π Complexes between Phosphaethyne and Hydrogen Chloride

Light induced reactions in cryogenic matrices (highlights 2021–2022)

Spectroscopic Identification and Photochemistry of Astrochemically Relevant Phosphorus-bearing Molecules [O, C, N, P] and [2O, C, N, P]

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Photochemistry of phosphenic chloride (ClPO2): isomerization with chlorine metaphosphite (ClOPO) and reduction by carbon monoxide

Abstract: Phosphenic chloride (ClPO2) is an elusive congener of nitryl chloride (ClNO2). By high-vacuum flash pyrolysis of 2-chloro-1,3,2-dioxaphospholane in the gas phase, ClPO2 has been efficiently generated and subsequently isolated in...

Cited by 3 publications

References 80 publications

Hydrogen-Bonded π Complexes between Phosphaethyne and Hydrogen Chloride

Hydrogen-Bonded π Complexes between Phosphaethyne and Hydrogen Chloride

Light induced reactions in cryogenic matrices (highlights 2021–2022)

Spectroscopic Identification and Photochemistry of Astrochemically Relevant Phosphorus-bearing Molecules [O, C, N, P] and [2O, C, N, P]

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Photochemistry of phosphenic chloride (ClPO₂): isomerization with chlorine metaphosphite (ClOPO) and reduction by carbon monoxide