A dash of protons: A theoretical study on the hydrolysis mechanism of 1-substituted silatranes and their protonated analogs

TitleA dash of protons: A theoretical study on the hydrolysis mechanism of 1-substituted silatranes and their protonated analogs
Publication TypeJournal Article
Year of Publication2012
AuthorsSok S, Gordon MS
Journal TitleComputational and Theoretical Chemistry
Volume987
Pages2-15
Date Published05
Type of ArticleArticle
ISBN Number2210-271X
Accession NumberWOS:000303098200002
Keywords1-aryloxysilatranes, 5-para-chlorophenyl silatrane, ab-initio, Acid catalyzed, bond, chemistry, gaussian-type basis, HYDROLYSIS, mechanism, molecular-orbital methods, mp2, ORGANIC-MOLECULES, pentacoordinate silicon-compounds, Ring cleavage, Silatrane, transannular interaction
Abstract

Ab initio calculations were carried out to study the hydrolysis mechanism of 1-substituted silatranes in the presence of an acid (acid-catalyzed) and an additional water (water-assisted). Compared with the neutral hydrolysis mechanism involving one water, use of an acid catalyst reduces the barrier associated with the rate-limiting step by approximate to 14 kcal/mol. A modest decrease of approximate to 5 kcal/mol is predicted when an additional water molecule is added to the neutral hydrolysis mechanism involving one water. The combination of an acid catalyst and an additional water molecule reduces the barrier by approximate to 27 kcal/mol. Bond order analysis suggests ring cleavage involving the bond breaking of a siloxane and silanol group during the neutral and acid-catalyzed hydrolysis of 1-substituted silatranes. respectively. Solvent effects, represented by the PCM continuum model, do not qualitatively alter computational gas-phase results. (C) 2011 Elsevier B.V. All rights reserved.

URL<Go to ISI>://WOS:000303098200002
DOI10.1016/j.comptc.2011.08.011
Alternate JournalComput. Theor. Chem.