Ab initio SCF-MO study of the Staudinger phosphorylation reaction between a phosphane and an azide to form a phosphazene

Citation
M. Alajarin et al., Ab initio SCF-MO study of the Staudinger phosphorylation reaction between a phosphane and an azide to form a phosphazene, J CHEM S P2, (9), 1999, pp. 1811-1814
Citations number
25
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
ISSN journal
03009580 → ACNP
Issue
9
Year of publication
1999
Pages
1811 - 1814
Database
ISI
SICI code
0300-9580(1999):9<1811:AISSOT>2.0.ZU;2-L
Abstract
The lowest energy pathway for a Staudinger reaction between a phosphane and an azide is predicted at the RHF and DFT ab initio SCF-MO level to proceed via an s-cis intermediate 7, followed by cyclisation and elimination of N- 2 to form a phosphazene. When suitable stabilising substituents are present , 7 can instead isomerise to the isolable s-trans intermediate 9. Natural b ond orbital perturbation theory analysis has been employed to identify the factors influencing the relative stability of the s-cis phosphazide and the s-trans isomers.