Conformation of Sterically Hindered 4-Methyl-2-oxo-2-trityl-1,3,2-dioxaphosphorinane in the Solid State and the Solution

Kruszyński, Rafał; Czubacka, Ewelina; Trzęsowska-Kruszyńska, Agata; Bartczak, Tadeusz J.; Bruzik, Karol S.; Knopik, P.; Kudzin, Zbigniew H.; Stec, Wojciech J.; Wolf, Wojciech M.

doi:10.1007/s10870-011-0102-y

Cited by 3 publications

(3 citation statements)

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“…(X = O, S, and Se) were investigated. The 1,3,2-dioxaphosphorinane derivatives are interesting compounds because of their biological activities [27,28]. Numerous studies of the structures and conformations of 1,3,2-dioxaphosphorinanes and related heterocycles have been reported [29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Structural, Electronic, Reactivity, and Conformational Features of 2,5,5-Trimethyl-1,3,2-diheterophosphinane-2-sulfide, and Its Derivatives: DFT, MEP, and NBO Calculations

et al. 2022

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In this study, we used density functional theory (DFT) and natural bond orbital (NBO) analysis to determine the structural, electronic, reactivity, and conformational features of 2,5,5-trimethyl-1,3,2-di-heteroatom (X) phosphinane-2-sulfide derivatives (X = O (compound 1), S (compound 2), and Se (compound 3)). We discovered that the features improve dramatically at 6-31G** and B3LYP/6-311+G** levels. The level of theory for the molecular structure was optimized first, followed by the frontier molecular orbital theory development to assess molecular stability and reactivity. Molecular orbital calculations, such as the HOMO–LUMO energy gap and the mapping of molecular electrostatic potential surfaces (MEP), were performed similarly to DFT calculations. In addition, the electrostatic potential of the molecule was used to map the electron density on a surface. In addition to revealing molecules’ size and shape distribution, this study also shows the sites on the surface where molecules are most chemically reactive.

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Section: Introductionmentioning

confidence: 99%

Structural, Electronic, Reactivity, and Conformational Features of 2,5,5-Trimethyl-1,3,2-diheterophosphinane-2-sulfide, and Its Derivatives: DFT, MEP, and NBO Calculations

et al. 2022

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“…Stereoelectronic effects were recognized in 1,3,2-dioxaphosphorinanes [12][13][14][15] bearing an alkoxy group on phosphorus. The axial disposition of both the tert-butyl and methoxy groups studied by X-ray diffraction analysis in 4-tert-butyl-2-methoxy-2-oxo-1,3,2-dioxaphosphorinan, and this conformation was illustrated by anomeric.…”

Section: Introductionmentioning

confidence: 99%

“…These variations in P-O bond distances are explained in terms of endo-anomeric and exo-anomeric effects[12][13][14][15]. The endo-anomeric effect is a dominant LP (2)O  σ* (P-X) negative hyperconjugation interaction between a pair of non-bonded electrons on oxygen and the adjacent P-X bond in axial conformer (Figure 3).…”

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confidence: 99%

Conformational Analysis of 2-halo-1,3,2-dioxaphosphinanes: A Density Functional Theory (DFT) Investigation

2020

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This research aimed at evaluating the stability of the 2-halo-1,3,2dioxaphosphinanes conformers at the LC-BLYP/aug-cc-pVTZ level of theory. The estimation of the total energy and the dipole moments of the axial and equatorial conformations were first done for the aforementioned molecules. Intermediate states of the transformations of the axial to equatorial conformer were determined. In the basis of the calculations, the axial conformer was found to be more stable than the equatorial conformer in these molecules. Transition states of these transformations were studied, as well. IN addition, the energetic and thermodynamics parameters of these transformations were investigated. Change of the P=O bond distances were illustrated with endo and exo-anomeric effects. The comparison of the P-O bond distances indicated the shorter bonds in the axial conformer compared to the equatorial conformer. These changes attributed to a dominant LP (2)O  σ* (P-X) negative hyperconjugation interaction between a pair of non-bonded electrons on oxygen and the adjacent P-X bond in axial conformer. The partitioning of the total electronic energy E(tot) into Lewis E(L) and non-Lewis E(NL) parts was performed using the concept of the natural bond orbital (NBO) analysis. Then, the natural coulomb electrostatic (NCE) potential energies, total energies into Lewis components, and total steric exchange energies were estimated. Calculations revealed that axial conformer was more stable than the equatorial conformer in the studied molecules. In addition, the barrier energy values of the transformations of axialboatequatorial conformers enhanced with decreasing the electronegativity of halogen. KEYWORDS 2-Halo-1,3,2-dioxaphosphinanes Anomeric effect Conformers Natural bond orbital analysis

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Conformational Analysis of 2-Methoxy-2-oxo-1,3,2-dioxaphosphorinane and Its Methylthio and Methylselenyl Analogues

Vafaei‐Nezhad

Ghiasi

Shafiei

2020

Russ. J. Phys. Chem.

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Conformation of Sterically Hindered 4-Methyl-2-oxo-2-trityl-1,3,2-dioxaphosphorinane in the Solid State and the Solution

Cited by 3 publications

References 79 publications

Structural, Electronic, Reactivity, and Conformational Features of 2,5,5-Trimethyl-1,3,2-diheterophosphinane-2-sulfide, and Its Derivatives: DFT, MEP, and NBO Calculations

Structural, Electronic, Reactivity, and Conformational Features of 2,5,5-Trimethyl-1,3,2-diheterophosphinane-2-sulfide, and Its Derivatives: DFT, MEP, and NBO Calculations

Conformational Analysis of 2-halo-1,3,2-dioxaphosphinanes: A Density Functional Theory (DFT) Investigation

Conformational Analysis of 2-Methoxy-2-oxo-1,3,2-dioxaphosphorinane and Its Methylthio and Methylselenyl Analogues

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