Generic placeholder image

Letters in Organic Chemistry

Editor-in-Chief

ISSN (Print): 1570-1786
ISSN (Online): 1875-6255

Research Article

The Investigation of Complexation Properties and Hard-Soft Acid-Base Relationship Between Thiacrown Ethers and Metal Ions

Author(s): Baki Çiçek and Ümit Çalışır

Volume 13, Issue 8, 2016

Page: [572 - 577] Pages: 6

DOI: 10.2174/1570178613666160906105300

Price: $65

Abstract

Background: There are numerious work on thiacrown ethers that are utilized for binding metal ions. Usually, relative binding ratios have been reported for few selected cations in these works. This study aims to develop a new method to explain cation binding properties by using the hardness parameters for ligands and metal ions, heteroatom rate (S/O) for ligands and extraction percentages.

Methods: In this work, complexation constants and selectivity factors of a previously synthesized mixed donor soft bases of thia-oxacrown ethers with metal salts hard Lewis acids (Mg2+, Ca2+, Cr3+), intermediate Lewis acids (Zn2+, Pb2+, Fe3+, Co2+), and soft Lewis acid (Ag+) were determined in a chloroformdichloromethane by using a liquid-liquid ion pairs metal extraction method.

Results: The synthesized compounds were 1,10-dithia-18-crown-6 (B1), 1,7-dithia-15-crown-5 (B2), 1,7-dithia-12-crown-4 (B3), 1,7-dithia-18-crown-6 (B4), 1,10-dithia-21-crown-7 (B5) and 1,4-dithia-12- crown-4 (B6). Based on various experiments using the aforementioned extraction method, following results have been observed: first, calcium ion has been the most extractable ion for all ligands in chloroform. At the same time, the most selective ligands for Zn+2, Mg2+, Ca2+, Fe3+, Cr3+, Co2+ and Pb2+in dichloromethane are B1, B1, B1, B1, B5, B5, B4-B5, respectively. Besides these results, in competitive liquid-liquid ion pairs metal extraction studies, all of the ligands have exhibited a large selectivity for iron and zinc ions.

Conclusion: In the light of results, one can conclude that the increase in the heteroatom rate in thiacrown ethers softens the ligands; therefore, the ligands complex with soft metals selectively.

Keywords: Thia crown ether, liquid-liquid ion pairs extraction, extraction percentage, selectivity factor, extraction constants.

Graphical Abstract

Rights & Permissions Print Export Cite as
© 2022 Bentham Science Publishers | Privacy Policy