Estimating pKa values for pentaoxyphosphoranes

被引：107

作者：

Davies, JE ^{[1
]}

Doltsinis, NL ^{[1
]}

Kirby, AJ ^{[1
]}

Roussev, CD ^{[1
]}

Sprik, M ^{[1
]}

机构：

[1] Univ Cambridge, Chem Lab, Cambridge CB2 1EW, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 23期

关键词：

D O I：

10.1021/ja025779m

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

pK(a) values are estimated independently, by two entirely different methods, for the ionizations of the apical and equatorial OH groups of two representative hydroxyphosphoranes. A bond length-pK(a) correlation based on crystal structures of cyclohexanol derivatives gives values of 13.5 +/- 1.5 and 8.62 +/- 1.87, respectively, for the apical and equatorial OH groups of tetracyclohexyloxyhydroxyphosphorane, and an ab initio molecular dynamics calculation gives values of 14.2 and 9.8 for the corresponding first ionizations of pentahydroxyphosphorane.

引用

页码：6594 / 6599

页数：6

共 29 条

[1] BOND LENGTH AND REACTIVITY - THE GAUCHE EFFECT - A COMBINED CRYSTALLOGRAPHIC AND THEORETICAL INVESTIGATION OF THE EFFECTS OF BETA-SUBSTITUENTS ON C-OX BOND LENGTH [J].