P(鈺怬)H to P鈥揙H Tautomerism: A Theoretical and Experimental Study

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• 作者：Benjamin G. Janesko ; Henry C. Fisher ; Mark J. Bridle ; Jean-Luc Montchamp
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：October 16, 2015
• 年：2015
• 卷：80
• 期：20
• 页码：10025-10032
• 全文大小：487K
• ISSN：1520-6904

文摘

Phosphinylidene compounds R¹R²P(O)H are important functionalities in organophosphorus chemistry and display prototropic tautomerism. Quantifying the tautomerization rate is paramount to understanding these compounds鈥?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)₂P(O)H > PhP(O) (OAlk)H > AlkP(O)(OAlk)H 鈮?(AlkO)₂P(O)H, where 鈥淎lk鈥?denotes an alkyl substituent. The combination of computational investigations with experimental validation establishes a quantitative measure for the reactivity of various phosphorus compounds, as well as an accurate predictive tool.