Premium
A DFT study on proton transfers in hydrolysis reactions of phosphate dianion and sulfate monoanion
Author(s) -
Yamabe Shinichi,
Zeng Guixiang,
Guan Wei,
Sakaki Shigeyoshi
Publication year - 2014
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23736
Subject(s) - chemistry , reactivity (psychology) , aryl , hydrolysis , medicinal chemistry , alcohol , transition state , phosphate , alkyl , proton , sulfate , molecule , hydronium , substrate (aquarium) , computational chemistry , organic chemistry , catalysis , oceanography , geology , medicine , alternative medicine , physics , pathology , quantum mechanics
B3LYP calculations were carried out on hydrolysis reactions of monosubstituted(R) phosphate dianion and sulfate monoanion. In the reacting system, water clusters (H 2 O) 22 and (H 2 O) 35 are included to trace reaction paths. For both P and S substrates with R = methyl group, elementary processes were calculated. While the phosphate undergoes the substitution at the phosphorus, the sulfate does at the methyl carbon. For the S substrate with R = neopentyl group, the product tert‐amyl alcohol was found to be formed via a dyotropic rearrangement from the neopentyl alcohol intermediate. For R = aryl groups, transition‐state geometries were calculated to be similar between P and S substrates. Calculated activation energies are in good agreement with experimental values. After the rate‐determining transition state of the substitution, the hydronium ion H 3 O + is formed at the third water molecule. It was suggested that alkyl and aryl substrates are of the different reactivity of the hydrolysis. © 2014 Wiley Periodicals, Inc.