Theoretical Investigation on the PCP(O) Linear Moiety: How to Stabilize Diphosphaallenic Derivatives

Density functional theory calculations on phosphavinylidene(oxo)phosphorane RP˭C˭P(˭O)R′ I are reported, where the R and R′ groups represent substituents with various electron-donor or electron-acceptor properties and different steric hindrance: H, F, Cl, OMe, SiH 3 , SiMe 3 , Me, Ph, Mes (2,4,6-tri...

Full description

Saved in:
Bibliographic Details
Published in:Phosphorus, sulfur, and silicon and the related elements sulfur, and silicon and the related elements, 2011-12, Vol.186 (12), p.2321-2331
Main Authors: Septelean, Raluca, Petrar, Petronela M., Nemes, Gabriela, Escudié, Jean, Silaghi-Dumitrescu, Ioan
Format: Article
Language:English
Subjects:
Density functional theory
DFT calculations
diphosphaallenes
Mathematical analysis
NBO analysis
phosphavinylidene(oxo)-phosphorane isomers
Steric hindrance
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Density functional theory calculations on phosphavinylidene(oxo)phosphorane RP˭C˭P(˭O)R′ I are reported, where the R and R′ groups represent substituents with various electron-donor or electron-acceptor properties and different steric hindrance: H, F, Cl, OMe, SiH 3 , SiMe 3 , Me, Ph, Mes (2,4,6-trimethylphenyl), and Mes* (2,4,6-tri-tert-butylphenyl) and R F 2,4,6-tris(trifluoromethyl)-phenyl. The investigations provide information about the groups that seem to be the best choice for the stabilization of such systems. The influence of the substituents' nature on the geometrical parameters and Wiberg bond orders for the P‒C bonds are discussed. Two isomers of I with a PCPO linkage (P≡C‒P(˭O)RR′ II and O˭P‒C≡PRR′ III) have also been studied. GRAPHICAL ABSTRACT
ISSN:1042-6507
1563-5325
DOI:10.1080/10426507.2011.597805