Theoretical study of the hydrolysis of chlorosilane

Gergo Szabó, D. Szieberth, L. Nyulászi

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The dependence of the mechanism of the SiCl bond hydrolysis on the number of the reacting water molecules was investigated in a comprehensive computational study on the prototype molecule H3SiCl. It has been established that the 1:1 reaction proceeds with retention of configuration at Si after a side on oxygen attack, via a 22-24 kcal/mol barrier in a nearly thermoneutral reaction. The barrier of the retention pathway drops to about 16 kcal/mol upon addition of one further water molecule, indicating a significant increase of the reaction rate with a small increase of the water concentration. With a further increase of the number of water molecules, the barrier of the retention process converges to ca. 15 kcal/mol. The barrier of the classical SN2 type reaction with a proton relay with at least three bridging water molecules from the attacking water to the leaving chloride ion drops below this value, depending on the number of the reactant water molecules, furthermore the reaction becomes clearly exothermic as the leaving chloride ion is complexed by the solvation of the available water molecules. A molecular dynamics study with 58 water molecules in the unit cell resulted in a 2 kcal/mol (free energy) barrier via an inversion pathway.

Original languageEnglish
Pages (from-to)231-238
Number of pages8
JournalStructural Chemistry
Volume26
Issue number1
DOIs
Publication statusPublished - 2015

Fingerprint

chlorosilanes
hydrolysis
Hydrolysis
Water
Molecules
water
molecules
Chlorides
chlorides
Ions
Energy barriers
Solvation
relay
Free energy
attack
Reaction rates
solvation
Molecular dynamics
Protons
ions

Keywords

  • Chlorosilane
  • DFT study
  • Hydrolysis
  • Mechanism
  • Molecular dynamics

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Theoretical study of the hydrolysis of chlorosilane. / Szabó, Gergo; Szieberth, D.; Nyulászi, L.

In: Structural Chemistry, Vol. 26, No. 1, 2015, p. 231-238.

Research output: Contribution to journalArticle

@article{1ff459421efd4dfcbfe277111d7c93a1,
title = "Theoretical study of the hydrolysis of chlorosilane",
abstract = "The dependence of the mechanism of the SiCl bond hydrolysis on the number of the reacting water molecules was investigated in a comprehensive computational study on the prototype molecule H3SiCl. It has been established that the 1:1 reaction proceeds with retention of configuration at Si after a side on oxygen attack, via a 22-24 kcal/mol barrier in a nearly thermoneutral reaction. The barrier of the retention pathway drops to about 16 kcal/mol upon addition of one further water molecule, indicating a significant increase of the reaction rate with a small increase of the water concentration. With a further increase of the number of water molecules, the barrier of the retention process converges to ca. 15 kcal/mol. The barrier of the classical SN2 type reaction with a proton relay with at least three bridging water molecules from the attacking water to the leaving chloride ion drops below this value, depending on the number of the reactant water molecules, furthermore the reaction becomes clearly exothermic as the leaving chloride ion is complexed by the solvation of the available water molecules. A molecular dynamics study with 58 water molecules in the unit cell resulted in a 2 kcal/mol (free energy) barrier via an inversion pathway.",
keywords = "Chlorosilane, DFT study, Hydrolysis, Mechanism, Molecular dynamics",
author = "Gergo Szab{\'o} and D. Szieberth and L. Nyul{\'a}szi",
year = "2015",
doi = "10.1007/s11224-014-0543-y",
language = "English",
volume = "26",
pages = "231--238",
journal = "Structural Chemistry",
issn = "1040-0400",
publisher = "Springer New York",
number = "1",

}

TY - JOUR

T1 - Theoretical study of the hydrolysis of chlorosilane

AU - Szabó, Gergo

AU - Szieberth, D.

AU - Nyulászi, L.

PY - 2015

Y1 - 2015

N2 - The dependence of the mechanism of the SiCl bond hydrolysis on the number of the reacting water molecules was investigated in a comprehensive computational study on the prototype molecule H3SiCl. It has been established that the 1:1 reaction proceeds with retention of configuration at Si after a side on oxygen attack, via a 22-24 kcal/mol barrier in a nearly thermoneutral reaction. The barrier of the retention pathway drops to about 16 kcal/mol upon addition of one further water molecule, indicating a significant increase of the reaction rate with a small increase of the water concentration. With a further increase of the number of water molecules, the barrier of the retention process converges to ca. 15 kcal/mol. The barrier of the classical SN2 type reaction with a proton relay with at least three bridging water molecules from the attacking water to the leaving chloride ion drops below this value, depending on the number of the reactant water molecules, furthermore the reaction becomes clearly exothermic as the leaving chloride ion is complexed by the solvation of the available water molecules. A molecular dynamics study with 58 water molecules in the unit cell resulted in a 2 kcal/mol (free energy) barrier via an inversion pathway.

AB - The dependence of the mechanism of the SiCl bond hydrolysis on the number of the reacting water molecules was investigated in a comprehensive computational study on the prototype molecule H3SiCl. It has been established that the 1:1 reaction proceeds with retention of configuration at Si after a side on oxygen attack, via a 22-24 kcal/mol barrier in a nearly thermoneutral reaction. The barrier of the retention pathway drops to about 16 kcal/mol upon addition of one further water molecule, indicating a significant increase of the reaction rate with a small increase of the water concentration. With a further increase of the number of water molecules, the barrier of the retention process converges to ca. 15 kcal/mol. The barrier of the classical SN2 type reaction with a proton relay with at least three bridging water molecules from the attacking water to the leaving chloride ion drops below this value, depending on the number of the reactant water molecules, furthermore the reaction becomes clearly exothermic as the leaving chloride ion is complexed by the solvation of the available water molecules. A molecular dynamics study with 58 water molecules in the unit cell resulted in a 2 kcal/mol (free energy) barrier via an inversion pathway.

KW - Chlorosilane

KW - DFT study

KW - Hydrolysis

KW - Mechanism

KW - Molecular dynamics

UR - http://www.scopus.com/inward/record.url?scp=84925482790&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84925482790&partnerID=8YFLogxK

U2 - 10.1007/s11224-014-0543-y

DO - 10.1007/s11224-014-0543-y

M3 - Article

VL - 26

SP - 231

EP - 238

JO - Structural Chemistry

JF - Structural Chemistry

SN - 1040-0400

IS - 1

ER -