Quantum Chemical Study of the Addition of Secondary Phosphine Chalcogenides to Vinyl Selenides

© 2020, Pleiades Publishing, Ltd. Abstract: DFT quantum chemical calculations at the B3PW91/6-31G(d) level of theory have shown that the addition of secondary phosphine sulfides and phosphine selenides with alkyl, phenyl, and phenylalkyl substituents to pentyl vinyl and hexyl vinyl selenides follows a molecular mechanism against the Markovnikov rule through energetically favorable eight-membered transition state, leading to the formation of tertiary phosphine chalcogenides. Secondary phosphine selenides are more reactive than the corresponding phosphine sulfides

Conformational Analysis of Dibutylphosphorylacetic Acid N,N-Dibutylamide in Solution

Abstract: Polarity of N,N-dibutylamide of dibutylphosphorylacetic acid has been determined and its conformational analysis has been carried out by the methods of dipole moments and quantum chemistry [DFT B3PW91/6-311++G(df,p)+CPCM]. In solution, this acetamide exists as conformational equilibrium of several forms with staggered gauche- and trans-orientations of the substituents relative to the P=O bond, in which intramolecular contacts are formed involving hydrogen atoms of butyl substituents at the nitrogen atom and the oxygen atom of the P=O group

Experimental and Theoretical Conformational Analysis of Tris(4-methylphenyl)phosphine and Its Chalcogenides

© 2020, Pleiades Publishing, Ltd. Abstract: Conformational analysis of tris(4-methylphenyl)phosphine and its oxide,sulfide, and selenide has been performed by the dipole moment method and DFTquantum chemical calculations at the B3PW91/ 6-311++G(df,p) level of theory. Thetitle compounds have been found to exist in solution as a single symmetricalconformer with gauche,gauche,gauche orientation ofthe substituents on the phosphorus atom with respect to the P=X bond (X = LEP,O, S, Se)

Polarity and Conformational Analysis of Tri(1-naphthyl)phosphine, Tri(2-naphthyl)phosphine, and Their Chalcogenides

Abstract: The polarity and structure of tri(1- or 2-naphthyl)phosphines and their chalcogenides were determined by the methods of dipole moments, IR spectroscopy, and DFT quantum-chemical calculations at the B3PW91/6-311++G(df,p) level of theory. In solution, tri(1-naphthyl)phosphine prefers a single conformer with a gauche,gauche,gauche orientation of the substituents at the phosphorus. Tri(2-naphthyl)phosphine, as well as both phosphine chalcogenides exist as equilibrium mixtures of several forms with a propeller arrangement of the substituents and a cis or gauche orientation of the Csp2‒Csp2 and P=X (X = LEP, O, S, Se) bonds