研究目的
To explore the photo-oxidation of PCl3 and POCl3 at low temperatures in Ar matrix using oxygen as a dopant, focusing on oxygen atom addition and insertion reactions through phosphadioxirane intermediates.
研究成果
The study demonstrates that 193 nm excimer photolysis of PCl3 and POCl3 with oxygen dopant in argon matrix leads to sequential oxygen addition and insertion reactions via phosphadioxirane intermediates, producing various phosphorus oxychlorides. Isotopic experiments and DFT computations confirm the reaction pathways and product identities, highlighting the role of singlet oxygen atoms and the uniqueness of the phosphadioxirane intermediate.
研究不足
The experiments are conducted at low temperatures in an argon matrix, which may not fully represent conditions in other environments. The use of specific laser wavelength (193 nm) limits the generalizability to other photolysis sources. Some spectral features could not be unambiguously assigned.
1：Experimental Design and Method Selection:
The study involved photolysis experiments using a 193 nm ArF excimer laser on PCl3 and POCl3 doped with oxygen in an argon matrix at low temperatures (12 K). Matrix isolation infrared spectroscopy was employed to monitor the reactions, and quantum chemical computations using DFT (B3LYP/6-311++G(d,p)) were used for structural assignments and energy calculations.
2：Sample Selection and Data Sources:
Samples included PCl3 and POCl3 with 5% O2 (natural 16O2 or 18O2) in argon matrix. Data were acquired through infrared spectral measurements before and after photolysis.
3：List of Experimental Equipment and Materials:
ArF excimer laser (193 nm), matrix isolation setup with cryostat for low temperatures, infrared spectrometer, PCl3, POCl3, O2 (16O2 and 18O2), argon gas.
4：Experimental Procedures and Operational Workflow:
Co-deposition of reactants (PCl3 or POCl3 with O2) in argon matrix at 12 K, followed by photolysis with 193 nm laser for 40 minutes. Infrared spectra were recorded before and after photolysis to identify photoproducts. Annealing experiments at 35 K were also performed.
5：Data Analysis Methods:
Infrared spectral features were assigned based on DFT-computed vibrational wavenumbers. Enthalpy changes and reaction barriers were calculated using DFT. Isotopic shifts with 18O2 were used to confirm product identities.
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