Ab initio study of some spectroscopic properties of PF2H

Tangou, B.; Caid, M. Ben; Barthelat, Jean‐Claude

doi:10.1016/0166-1280(91)85113-l

Cited by 4 publications

(2 citation statements)

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Section: Experimental and Methodsmentioning

confidence: 99%

“…Polarization functions for the B1 basis set had the following zeta values: oxygen (0.85), nitrogen (0.95), phosphorus (0.45), and carbon (0.8). The use of B1 basis set despite its small size is justified because it gave satisfactory results in describing the properties of PF 2 H. 36 Theoretical calculations dealt only with compound 1b with R = CH 3 . We checked that all the optimized structures corresponded to minimum energy values on the potential energy surface (PES) for all stable compounds (no imaginary frequency), or a saddle point (a single imaginary frequency).…”

Section: Modeling Methodsmentioning

confidence: 99%

See 1 more Smart Citation

New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation

Méjri

Fliss

Essalah

et al. 2022

Int J of Quantum Chemistry

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Oxidative addition of aliphatic amine on monocyclic 2-R-1,3,2-dioxaphospholane (R = methyl or phenyl) leading to phosphoranes bearing a P H axial bond was investigated using a combined theoretical and experimental approach. The reaction followed first order kinetics for both reactants. The activation parameters were consistent with a concerted mechanism exhibiting stereo, enantio, and regio specificities.Systematic density functional theory studies including reactivity descriptors, structural parameters, determination of all possible phosphorane isomers, their transition states and their formation mechanisms were carried out to delineate the reaction pathway. Depending on the nature of the atom in the final apical position (H, N of the amine, or C of the methyl), three types of phosphoranes were identified. Energy profiles, using the intrinsic reaction coordinate technique for the formation of each isomer, were established. It was shown that the phosphorus biphilicity acts in three consecutive sequences, namely nitrogen nucleophilic attack leading to a supermolecule structure, nucleophilic behavior of phosphorus in the transition state zone of influence, and electrophilic approach of the nitrogen atom to complete the reaction. Phosphorane with an equatorial P H bond was found to be a kinetic product that transforms rapidly to the thermodynamically stable isomer with axial P H via two consecutive Berry pseudo-rotations. A new tool, referred to reactive internal reaction coordinates, was introduced to represent the reaction path more clearly.

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Section: Experimental and Methodsmentioning

confidence: 99%

Section: Modeling Methodsmentioning

confidence: 99%