Exchange reactions of chloriranium and chlorirenium ions: a G2 investigation

Theis I. Sølling; Leo Radom

doi:10.1016/S1387-3806(98)14138-6

Exchange reactions of chloriranium and chlorirenium ions: a G2 investigation

Theis I. Sølling, Leo Radom^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Ab initio molecular orbital calculations at the G2 level have been used to study exchange reactions between cationic three-membered chlorine heterocycles and unsaturated hydrocarbons. The reactions are predicted to proceed with little or no overall barrier. The relationship of the theoretical findings to relevant experimental observations is discussed. The electronic characteristics of the exchange transition structures are compared with those for the analogous sulfur and phosphorus systems. The structures can be understood qualitatively in terms of a principal interaction resembling the triple-ion configuration found for S_N2 transition structures and a secondary back-bonding interaction.

Original language	English
Pages (from-to)	263-270
Number of pages	8
Journal	International Journal of Mass Spectrometry
Volume	185
DOIs	https://doi.org/10.1016/S1387-3806(98)14138-6
State	Published - 29 Apr 1999
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 1999 Elsevier Science B.V.

Keywords

Back bonding
Exchange
G2 theory
Three-membered heterocyclic ions
π interactions

ASJC Scopus subject areas

Instrumentation
Condensed Matter Physics
Spectroscopy
Physical and Theoretical Chemistry

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10.1016/S1387-3806(98)14138-6

Cite this

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title = "Exchange reactions of chloriranium and chlorirenium ions: a G2 investigation",

abstract = "Ab initio molecular orbital calculations at the G2 level have been used to study exchange reactions between cationic three-membered chlorine heterocycles and unsaturated hydrocarbons. The reactions are predicted to proceed with little or no overall barrier. The relationship of the theoretical findings to relevant experimental observations is discussed. The electronic characteristics of the exchange transition structures are compared with those for the analogous sulfur and phosphorus systems. The structures can be understood qualitatively in terms of a principal interaction resembling the triple-ion configuration found for SN2 transition structures and a secondary back-bonding interaction.",

keywords = "Back bonding, Exchange, G2 theory, Three-membered heterocyclic ions, π interactions",

author = "S{\o}lling, \{Theis I.\} and Leo Radom",

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year = "1999",

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doi = "10.1016/S1387-3806(98)14138-6",

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TY - JOUR

T1 - Exchange reactions of chloriranium and chlorirenium ions

T2 - a G2 investigation

AU - Sølling, Theis I.

AU - Radom, Leo

PY - 1999/4/29

Y1 - 1999/4/29

N2 - Ab initio molecular orbital calculations at the G2 level have been used to study exchange reactions between cationic three-membered chlorine heterocycles and unsaturated hydrocarbons. The reactions are predicted to proceed with little or no overall barrier. The relationship of the theoretical findings to relevant experimental observations is discussed. The electronic characteristics of the exchange transition structures are compared with those for the analogous sulfur and phosphorus systems. The structures can be understood qualitatively in terms of a principal interaction resembling the triple-ion configuration found for SN2 transition structures and a secondary back-bonding interaction.

AB - Ab initio molecular orbital calculations at the G2 level have been used to study exchange reactions between cationic three-membered chlorine heterocycles and unsaturated hydrocarbons. The reactions are predicted to proceed with little or no overall barrier. The relationship of the theoretical findings to relevant experimental observations is discussed. The electronic characteristics of the exchange transition structures are compared with those for the analogous sulfur and phosphorus systems. The structures can be understood qualitatively in terms of a principal interaction resembling the triple-ion configuration found for SN2 transition structures and a secondary back-bonding interaction.

KW - Back bonding

KW - Exchange

KW - G2 theory

KW - Three-membered heterocyclic ions

KW - π interactions

UR - https://www.scopus.com/pages/publications/0007792305

U2 - 10.1016/S1387-3806(98)14138-6

DO - 10.1016/S1387-3806(98)14138-6

M3 - Article

AN - SCOPUS:0007792305

SN - 1387-3806

VL - 185

SP - 263

EP - 270

JO - International Journal of Mass Spectrometry

JF - International Journal of Mass Spectrometry

ER -

Exchange reactions of chloriranium and chlorirenium ions: a G2 investigation

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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