University of Oulu

Complexation of N-heteroaromatic cations with crown ethers and tetraphenylborate

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Author: Kiviniemi, Sari1
Organizations: 1University of Oulu, Faculty of Science, Department of Chemistry
Format: ebook
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 1.3 MB)
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Language: English
Published: 2001
Publish Date: 2001-05-14
Thesis type: Doctoral Dissertation
Defence Note: Academic Dissertation to be presented with the assent of the Faculty of Science, University of Oulu, for public discussion in Kajaaninsali (Auditorium L6), Linnanmaa, on June 21st, 2001, at 12 noon.
Reviewer: Professor Harri Lönnberg
Professor Jouko Vepsäläinen


Study was made of host-guest complexation of neutral crown ethers with five- and six-membered N-heteroaromatic cations and purinium cation. Complexation of tetraphenylborate with selected N-heteroaromatic cations and tropylium cation also was studied.

Crown ether complexes were characterized by mass spectrometric and ¹H NMR spectrometric methods and by X-ray crystallography. Fast atom bombardment mass spectrometry (FABMS) was used as a prelimary tool to characterize the complexes and electrospray ionization mass spectrometry (ESIMS) was used to confirm the complexation stoichiometry. Crystal structures were determined by X-ray crystallography to study the complexation in solid state, and stability constants were measured in acetonitrile by ¹H NMR titration at 30 °C to study the complexation in solution. Mass spectrometric studies indicated preferential 1:1 complexation stoichiometry between crown ethers and N-heteroaromatic cations. Crystal structures of crown ether complexes showed that hydrogen bonding and to a lesser degree cation-π and π-π interactions stabilize the structures in solid state. The values of stability constants for crown ether complexes with N-heteroaromatic cations and purinium cation varied between 10 and 350 M⁻¹. Stability constants were higher for complexes with six-membered N-heteroaromatic cations and purinium cation than for complexes with five-membered cations. The values indicated that hydrogen bonding was the main interaction in solution.

Tetraphenylborate formed complexes with four N-heteroaromatic cations and tropylium cation, and reacted with six N-heteroaromatic cations through the displacement of one phenyl group by N-heterocycle to form triphenylboranes. The complexes and displacement products were characterized by ¹H NMR spectrometry. Four crystal structures of complexes and three crystal structures of displacement products were resolved. Stability constants of complexes were measured in methanol/acetonitrile (1:1) solution at 30 °C by ¹H NMR titration method. The values of stability constants for tetraphenylborate complexes with N-heteroaromatic cations ranged from 10 to 50 M⁻¹. C-H···π and N-H···π interactions were found to stabilize the structures both in solid state and in solution.

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Series: Acta Universitatis Ouluensis. A, Scientiae rerum naturalium
ISSN-E: 1796-220X
ISBN: 951-42-5997-1
ISBN Print: 951-42-5996-3
Issue: 366
Copyright information: © University of Oulu, 2001. This publication is copyrighted. You may download, display and print it for your own personal use. Commercial use is prohibited.