Abstract
We report the preparation of four new double-bridged PNP-lariat ether derivatives L1–L4 synthesized from precursor 1 by the subsequent substitution of chlorine atoms. The process consists of two steps. In the first one two reactive chlorine atoms of the –PCl2 exocyclic moiety are substituted with respective nucleophiles: 2,2′-thiodiethanethiol 2 and 2,2′-oxydiethanethiol 3. In the second step the other chlorine atoms are substituted by aziridynyl 6 and pyrrolidinyl 7 groups, respectively. Their structures were established by MS, 1H NMR, 31P NMR, 13C NMR spectroscopy. Furthermore, this work includes the investigation of complexation of silver(I) ions with the new ligands L1–L4 in methanol solution. The formation of the novel tetra-nuclear silver(I) complexes were observed. Stability constants were determined using a simple potentiometric titration. 1H NMR, 31P NMR, 13C NMR spectra were recorded to investigate how the complexation of silver(I) ions by the investigated macrocyclic ligands occurs.
Highlights
Lariat ethers are group of compounds still considered to be attractive research objects.[1,2,3,4] The term “lariat ether” refers to a crown ether having a side chain attached to the crown moiety by the so-called pivot atoms (C, N or P)
We report the preparation of four new double-bridged PNP-lariat ether derivatives L1–L4 synthesized from precursor 1 by the subsequent substitution of chlorine atoms
The weaker N–Ag+ interaction gives the possibility of stronger binding of the cation by oxygen donor atoms from crown ether moiety of the ligand
Summary
Lariat ethers are group of compounds still considered to be attractive research objects.[1,2,3,4] The term “lariat ether” refers to a crown ether having a side chain attached to the crown moiety by the so-called pivot atoms (C, N or P). The subjects of this publication are the P-pivot lariat ether derivatives This is the class of reactive crown ethers which was formed by cyclocondensation of hexachlorocyclotriphosphazene with tetraethylene glycol in the presence of sodium hydride.[14,15] The closure of the ring was assisted by the sodium cation which served as a template.[16,17] The interaction with ve oxygen donors of the polyether substrate which wrapped itself around the alkali metal cation satis es its coordination requirements, thereby favouring ring closure to form the macrocycle.[18] This type of lariat ethers may be regarded as “intelligent substrate” because it possesses reactive sites capable for spontaneous self assembling with molecular complementary reagents. This compound has the reactive chloride substituents, capable of undergoing various
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