The interactions of cyclophosphazenes with olefin containing exocyclic groups

被引：6

作者：

Calichman, M ^{[1
]}

Hernandez-Rubio, D ^{[1
]}

Allen, CW ^{[1
]}

机构：

[1] Univ Vermont, Dept Chem, Burlington, VT 05405 USA

来源：

PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS | 2002年 / 177卷 / 6-7期

关键词：

cyclophosphazenes; DFT calculations; NMR; photoelectron spectroscopy;

D O I：

10.1080/10426500212247

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional calculations on the series N3P3F5R(R=CH2CH3, CH=CH2, Cequivalent toCH) show that the phosphazene substituent effect is similar to that of CF3 and is dominated by a bondpolarity. UV-photoelectron measurements also favor a a bond polarization effect. Calculations on N3P3F5ECH=CH2 (E=Q, CH2) and photoelectron spectroscopy of the vinyloxy derivative show the strong electronic effect of the phosphazene, which is dominated by the a bond polarization mechanism. Extensive NMR correlations for substituted vinyloxy phosphazenes indicate the sensitivity of these effects to the nature of the ring substituents. The reactivity ratio and NMR data for styryloxy phosphazenes demonstrate the absence of significant mesomeric interactions.

引用

页码：1811 / 1813

页数：3