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Quantum chemical calculation of amino‐substituted but‐2‐yne dications: Distonic and gitonic character?
Author(s) -
Kottmann Jakob,
Wassiljew Olga,
Drandarov Konstantin,
Kantlehner Willi,
Siehl HansUllrich
Publication year - 2014
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3232
Subject(s) - chemistry , dication , steric effects , quantum chemical , tetraphenylborate , computational chemistry , tetrafluoroborate , quantum chemistry , electronic structure , ion , crystallography , supramolecular chemistry , stereochemistry , molecule , crystal structure , organic chemistry , ionic liquid , catalysis
The tetrakis‐dimethylamino substituted but‐2‐yne dication 1 and related model cations are investigated by DFT, MP2, CCSD and CCSD(T)) quantum chemical calculations to elucidate structural and electronic details, energy barriers and conformational preferences in order to rationalize experimental NMR‐spectra and crystallographic structural data of tetrafluoroborate and tetraphenylborate salts of 1 . Very small energy differences (<2 kJ mol −1 ) between different conformations are caused by electronic and steric effects in the cation. In addition, solid‐state effects such as anion cation interactions may lead to conformational differences in the salts. In dication 1 and analogous model cations, the distonic arrangement of the charges is preferred over a gitonic configuration. Copyright © 2013 John Wiley & Sons, Ltd.