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Issue 45, 2015
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A fluorosurfactant and photoreducible CuII-tren click catalyst: surfactant and catalytic properties at liquid/liquid interfaces

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Abstract

The fluorous copper(II) complex [CuII(trenRf6)3-benzoylbenzoate]3-benzoylbenzoate 2, composed of a highly fluorophilic tris(2-aminoethyl)amine ligand and two 3-benzoylbenzoates as counterions and photosensitizers, was synthesized from the dinuclear complex [CuII2(3-benzoylbenzoate)4(H2O)2] 1 which was characterized by X-ray analysis. Complex 2, which is highly soluble in perfluorocarbons, moderately soluble in organic solvents while insoluble in water, was found to be a very effective fluorosurfactant. At the air/water interface it formed a Langmuir film, which upon compression slowly collapsed at about 28 mN m−1, which corresponds to a surface area of about 220 Å2 per molecule. Tensiometric measurements revealed that 2 is more rapidly adsorbed at the diisopropyl ether (DIPE)/water interface than the perfluorodecalin (PFD)/water one, leading to a decrease of the interfacial tensions of about 14 mN m−1 and 40 mN m−1, respectively. Photoreduction of 2 occurs effectively in H-donating solvents such as THF and DIPE, or even in PFD ensuring that an electron donor, such as propargyl alcohol, is present in a separate aqueous phase. Complex 2, when combined with light (365 nm), catalyzes the click reaction between the azide 3 and alkyne 4 under homogeneous conditions (methanol), to afford the disaccharide 5. Under emulsified biphasic DIPE/water or PFD/water conditions, the reactions proceeded well. However, it was shown that a fast and significant amount of copper and 3-benzoylbenzoate counterion was transferred into the aqueous phase, and that most of the catalysis could be ascribed to a copper species solubilised in the aqueous phase, and not to the fluorous copper complex accumulated at the interface.

Graphical abstract: A fluorosurfactant and photoreducible CuII-tren click catalyst: surfactant and catalytic properties at liquid/liquid interfaces

  • This article is part of the themed collection: Fluorine
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Publication details

The article was received on 29 May 2015, accepted on 14 Oct 2015 and first published on 14 Oct 2015


Article type: Paper
DOI: 10.1039/C5DT02039E
Citation: Dalton Trans., 2015,44, 19700-19707

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    A fluorosurfactant and photoreducible CuII-tren click catalyst: surfactant and catalytic properties at liquid/liquid interfaces

    Q. Jochyms, P. Guillot, E. Mignard and J. Vincent, Dalton Trans., 2015, 44, 19700
    DOI: 10.1039/C5DT02039E

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