Issue 5, 2009
From the journal:

Dalton Transactions

Lariat ethers with fluoroaryl side-arms: a study of CF⋯metal cation interaction in the complexes of N-(o-fluoroaryl)azacrown ethers†

Petr K. Sazonov,*a   Lidiya Kh. Minacheva,b   Andrei V. Churakov,b   Vladimir S. Sergienko,b   Galina A. Artamkina,a   Yuri F. Oprunenkoa  and  Irina P. Beletskaya*a  

* Corresponding authors

a Chemistry Department of the M. V. Lomonosov Moscow State University, 119992 Moscow
E-mail: beletska@org.chem.msu.ru
Fax: +7 495 939 3618

b N. S. Kurnakov Institute of General and Inorganic Chemistry RAS, 119991 Moscow
E-mail: min@igic.ras.ru
Fax: +7 495 954 1279

Abstract

New lariat ethers, N-(o-fluorophenyl)aza-15-crown-5 (F-A15C5) and N,N′-bis(o-fluorophenyl)diaza-18-crown-6 (F2-A218C6), were prepared by the N-arylation of the corresponding azacrown ethers. The interaction of the ligands with metal cations was studied in solution by 1H and 19F NMR (in acetone-d6) and UV spectroscopy (MeOH) confirming the formation of complexes of F2-A218C6 with K+, Na+, Ag+, Ba2+, Pb2+ and of F-A15C5 with Na+ and giving evidence of CF⋯metal cation interaction. Cation binding constants (β, evaluated by UV titration method), demonstrate that F-A15C5 and F2-A218C6 form more stable complexes than their fluorine-free analogs. The effect depends on the nature of the metal cation and is at a maximum for hard, singly charged cations (up to 3 logβ units for K+ complex of F2-A218C6). The X-ray structures of complexes [Pb(F2-A218C6)(H2O)](ClO4)2 (1) and [Ba(F2-A218C6)(ClO4)2] (2) reveal short Pb–F (2.805 Å) and Ba–F (2.965 Å) contacts. Complex 2 is centrosymmetric (Ci), while complex 1 has C2 symmetry with one-side coordination of o-fluorophenyl groups to Pb2+. This “one-side” coordination mode of Pb2+ is indicative of a partial localization of the Pb2+ lone pair.

Graphical abstract: Lariat ethers with fluoroaryl side-arms: a study of CF⋯metal cation interaction in the complexes of N-(o-fluoroaryl)azacrown ethers

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Article information

DOI
https://doi.org/10.1039/B807199C
Article type
Paper
Submitted
28 Apr 2008
Accepted
10 Oct 2008
First published
04 Dec 2008

Dalton Trans., 2009, 843-850

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Lariat ethers with fluoroaryl side-arms: a study of CF⋯metal cation interaction in the complexes of N-(o-fluoroaryl)azacrown ethers

P. K. Sazonov, L. Kh. Minacheva, A. V. Churakov, V. S. Sergienko, G. A. Artamkina, Y. F. Oprunenko and I. P. Beletskaya, Dalton Trans., 2009, 843 DOI: 10.1039/B807199C

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