P(=O)H to P-OH Tautomerism: A Theoretical and Experimental Study

被引：141

作者：

Janesko, Benjamin G. ^{[1
]}

Fisher, Henry C. ^{[1
]}

Bridle, Mark J. ^{[1
]}

Montchamp, Jean-Luc ^{[1
]}

机构：

[1] Texas Christian Univ, Dept Chem, Ft Worth, TX 76129 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 20期

基金：

美国国家科学基金会;

关键词：

CORRELATED MOLECULAR CALCULATIONS; DENSITY-FUNCTIONAL THEORY; GAUSSIAN-BASIS SETS; PHOSPHINE-OXIDE; H-BOND; HYDROPHOSPHORYL COMPOUNDS; PHOSPHORUS-COMPOUNDS; AB-INITIO; ACID; MECHANISM;

D O I：

10.1021/acs.joc.5b01618

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Phosphinylidene compounds (RRP)-R-1-P-2(O)H are important functionalities in organophosphorus chemistry and display prototropic tautomerism. Quantifying the tautomerization rate is paramount to understanding these compounds' tautomerization behavior, which may impact their reactivities in various reactions. We report a combined theoretical and experimental study of the initial tautomerization rate of a range of phosphinylidene compounds. Initial tautomerization rates are found to decrease in the order H3PO2 > Ph2P(O)H (PhO)(2)P(O)H > PhP(O) (OAlk)H > AlkP(O)(OAlk)H approximate to (AlkO)(2)P(O)H, where "Alk" denotes an alkyl substituent. The combination of computational investigations establishes a quantitative measure for the reactivity of various phosphorus compounds, as well as with experimental validation an accurate predictive tool.

引用

页码：10025 / 10032

页数：8

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