Mechanisms of Substitution Reactions at Phosphorus. XII. A Kinetic Study of the Decomposition of Quaternary Phosphonium Hydroxides

Hydroxide Degradation Pathways for Substituted Benzyltrimethyl Ammonium: A DFT Study

“…The R-value for this fit is 0.97, showing a much better linear relationship than the single-meta substitution case. Still, the impact on stability is far less than the singly substituted phosphonium ions reported by McEwen et al 25 For the para substitutions, the benzyl S N 2 log(k/k 0 ) vs. σ para plot (Fig. S3a) shows no linear relationship.…”

“…It has been reported that hydroxide degradation of substituted quaternary phosphonium cations showed a linear relationship between log(k/k 0 ) and σ with a slope of 3.64. 25 Encouraged by this research that showed a change of stability of 4 orders of magnitude in stability between singly substituted phosphoium ions, we employed a similar approach to search for substituent groups that might result in improved degradation barriers. For the neutral para substitutions, when the reaction TS structure has positive or negative charges, σ para + or σ para − values should be used instead of σ para .…”

Nucleophilic arylation with tetraarylphosphonium salts

“…The alkaline hydrolysis of phosphonium salts has been well-studied for the past decades 30 39 40 41 42 43 44 45 46 47 . As a third-order reaction (first order with respect to phosphonium salt, second order to hydroxide) 40 41 , the alkaline hydrolysis of tetraphenylphosphonium salt would lead to the formation of triphenylphosphine oxide (Ph 3 PO) (refs 46 , 48 ).…”

Extraction of Wheat Straw with Aqueous Tetra-n-Butylphosphonium Hydroxide

“…1. The decomposition mechanisms of phosphonium hydroxides were discussed by McEwen et al (1965) already in the 1960's. There is a growing interest in the use of ILs other than the imidazolium-based systems, due to the reactivity of the imidazolium cation (Ebner et al 2008;King et al 2012).…”