Phosphoryl chloride–methanol adducts: Matrix isolation infrared and DFT studies

Ramanathan, N.; Sankaran, K.

doi:10.1016/j.molstruc.2013.09.057

Cited by 18 publications

(12 citation statements)

References 70 publications

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“…The analysis of the infrared spectra as a result of photolysis divulged the formation of POCl 3 as one of the major products. The spectral features observed at 1315.4/1312.8/1310.4 and 590.5/589.5 cm −1 correspond to P=O and P−Cl stretching modes of POCl 3 , respectively, in Ar matrix . When experiments were performed with 18 O 2 , the P=O stretching features were shifted to 1270.3/1267.8/1265.8 cm −1 with a barely perceptible shift for the P−Cl stretching mode.…”

Section: Resultssupporting

confidence: 64%

Photolysis of PCl₃/POCl₃ with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

et al. 2019

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Photolysis was performed on PCl 3 and POCl 3 in the presence of oxygen dopant in Ar matrix at low temperatures using 193 nm ArF excimer laser. The photo irradiation initially facilitated the formation of ozone in situ in the low temperature matrix. For PCl 3 + O 2 photolysis with 193 nm ArF excimer, initially POCl 3 was produced and subsequent oxygen atom insertion on POCl 3 generated PO 2 Cl 3 . Furthermore, secondary reaction channel opens up in PCl 3 + O 2 photolysis to form a variety of photoproducts such as POCl, P III O 2 Cl, P V O 2 Cl and PO 3 Cl. The insertion of oxygen atom on POCl through phosphadioxirane intermediate generated P III O 2 Cl and the direct oxygen atom addition resulted in P V O 2 Cl. A successive oxygen insertion on P V O 2 Cl triggered the PO 3 Cl generation. The identification of all the photoproducts was confirmed through 18 O 2 isotopic experiments and quantum chemical computations performed using density functional theory (DFT). Computations carried out at B3LYP level of theory with 6-311 + + G(d,p) basis set were used to correlate the structure of photo products obtained experimentally. Interestingly, photo irradiation of POCl 3 with oxygen dopant in Ar matrix @193 nm ArF excimer resulted in the generation of PO 2 Cl 3 , PO 3 Cl 3 and PO 4 Cl 3 photo products by a sequential insertion of oxygen atoms through phosphadioxirane intermediate. A compelling evidence for the passage of the reaction through phosphadioxirane intermediate is established through 18 O 2 isotopic substitution experiments.

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Section: Resultssupporting

confidence: 64%

Photolysis of PCl₃/POCl₃ with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

et al. 2019

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“…Parts A and B of Figure correspond to the O–H and C–O stretching regions of CH 3 OH in N 2 matrix. The υ 1 O–H and υ 8 C–O stretching mode of CH 3 OH was observed at 3663.4 and 1034.4 cm –1 , respectively. , The features observed at 3653.8, 3651.1, and 3649.0 cm –1 in the υ 1 mode and at 1032.2 cm –1 in the υ 8 mode are due to methanol dimer in N 2 matrix. − On variation of the concentration of C 4 H 5 N in N 2 matrix, a small feature in the υ 1 mode appears as a shoulder at 3661.5 cm –1 and a new peak observed in the υ 8 mode at 1027.9 cm –1 shows concentration dependence and increases in intensity.…”

Section: Experimental and Computational Detailsmentioning

confidence: 98%

Effect of Methyl Substitution on the N–H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies

2018

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Hydrogen-bonded interactions of pyrrole with water and methanol have been studied using matrix isolation infrared spectroscopy and compared with the calculation performed on dimethyl ether. Computations carried out at MP2/aug-cc-pVDZ level of theory yielded two minima for the pyrrole-water and pyrrole-methanol complexes. The global and local minima correspond to the N-H···O and O-H···π complexes, respectively, where the N-H group of pyrrole interacts with oxygen of water/methanol and O-H of water and methanol interacts with the π cloud of pyrrole. Computations performed on the pyrrole-dimethyl ether gave only N-H···O type complex. From the experimental vibrational wavenumber shifts in the N-H stretching and N-H bending modes of pyrrole, as well as in the O-H stretching modes of water and methanol, the 1:1 N-H···O complexes were discerned. The strength of the N-H···O hydrogen bond and the corresponding shift in the N-H stretching vibrational wavenumbers increases in the order pyrrole-water < pyrrole-methanol < pyrrole-dimethyl ether, where a proton is successively replaced by a methyl group. Apart from the 1:1 complexes, higher clusters of 2:1 and 1:2 pyrrole-water and pyrrole-methanol complexes were also generated in N matrix. Atoms in molecules and natural bond orbital analyses were carried out at the MP2/aug-cc-pVDZ level to understand the nature of interaction in the 1:1 pyrrole-water, pyrrole-methanol and pyrrole-dimethyl ether complexes.

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“…Figure a shows the infrared spectrum in the regions 3670–3640 cm –1 (grid A) and 1060–1020 cm –1 (grid B), where O–H and O–C stretching vibrational modes of CH 3 OH appear. The O–H stretch of CH 3 OH occurs at 3663.5 cm –1 in a nitrogen matrix. − In the codeposition experiment of PCl 3 and CH 3 OH, a new feature appeared at 3650.0 cm –1 , as shown in Figure b–d (grid A). The feature observed at 1034.0 cm –1 corresponds to the O–C stretch of monomeric CH 3 OH .…”

Section: Resultsmentioning

confidence: 97%

“…The study on noncovalent interaction in POCl 3 :CH 3 OH adducts has recently been reported . The adduct stabilized by H-bonding interaction (between H of CH 3 OH and Cl of POCl 3 ) was the global minimum, which was experimentally identified in the low temperature N 2 matrix.…”

Section: Resultsmentioning

confidence: 99%

Evidence for Phosphorus Bonding in Phosphorus Trichloride–Methanol Adduct: A Matrix Isolation Infrared and ab Initio Computational Study

et al. 2015

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The weak interaction between PCl3 and CH3OH was investigated using matrix isolation infrared spectroscopy and ab initio computations. In a nitrogen matrix at low temperature, the noncovalent adduct was generated and characterized using Fourier transform infrared spectroscopy. Computations were performed at B3LYP/6-311++G(d,p), B3LYP/aug-cc-pVDZ, and MP2/6-311++G(d,p) levels of theory to optimize the possible geometries of PCl3-CH3OH adducts. Computations revealed two minima on the potential energy surface, of which, the global minimum is stabilized by a noncovalent P···O interaction, known as a pnictogen bonding (phosphorus bonding or P-bonding). The local minimum corresponded to a cyclic adduct, stabilized by the conventional hydrogen bonding (Cl···H-O and Cl···H-C interactions). Experimentally, 1:1 P-bonded PCl3-CH3OH adduct in nitrogen matrix was identified, where shifts in the P-Cl modes of PCl3, O-C, and O-H modes of CH3OH submolecules were observed. The observed vibrational frequencies of the P-bonded adduct in a nitrogen matrix agreed well with the computed frequencies. Furthermore, computations also predicted that the P-bonded adduct is stronger than H-bonded adduct by ∼1.56 kcal/mol. Atoms in molecules and natural bond orbital analyses were performed to understand the nature of interactions and effect of charge transfer interaction on the stability of the adducts.

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Phosphoryl chloride–methanol adducts: Matrix isolation infrared and DFT studies

Cited by 18 publications

References 70 publications

Photolysis of PCl₃/POCl₃ with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

Photolysis of PCl₃/POCl₃ with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

Effect of Methyl Substitution on the N–H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies

Evidence for Phosphorus Bonding in Phosphorus Trichloride–Methanol Adduct: A Matrix Isolation Infrared and ab Initio Computational Study

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Phosphoryl chloride–methanol adducts: Matrix isolation infrared and DFT studies

Cited by 18 publications

References 70 publications

Photolysis of PCl3/POCl3 with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

Photolysis of PCl3/POCl3 with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

Effect of Methyl Substitution on the N–H···O Interaction in Complexes of Pyrrole with Water, Methanol, and Dimethyl Ether: Matrix Isolation Infrared Spectroscopy and ab Initio Computational Studies

Evidence for Phosphorus Bonding in Phosphorus Trichloride–Methanol Adduct: A Matrix Isolation Infrared and ab Initio Computational Study

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Photolysis of PCl₃/POCl₃ with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway

Photolysis of PCl₃/POCl₃ with Oxygen Dopant Using 193 nm ArF Excimer at Low Temperatures: Oxygen Insertion through ‘Phosphadioxirane’ Pathway