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Issue 45, 2011
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Further insight into the coordination of 2,5-dicarbothioamidopyrroles: the case of Cu and Co complexes

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Abstract

The coordination chemistry of 2,5-dicarbothioamidopyrrole ligands, namely N2,N5-dibutyl-3,4-diphenyl-1H-pyrrole-2,5-bis(carbothioamide) and N2,N5,3,4-tetraphenyl-1H-pyrrole-2,5-bis(carbothioamide), has been investigated with Cu(II) metal centres by means of X-ray crystallography. This resulted in the formation of the expected planar S,N,S′ coordinated complex for the former ligand and unexpected ring-closure reactions, with formation of benzothiazole sidearms, for the latter. Both Cu(II) and Cu(I), used in large excess, were found to favour the ring-closure reaction, although the structural characterisation of the resulting complexes contained only Cu(II) cations, with varying coordination geometries ranging from square planar and square-based pyramidal to tetrahedral. By repeating the reaction using a slight excess of Cu(II) (2 : 1) two more different structures were obtained where the metal was coordinated to the original ligand, N2,N5,3,4-tetraphenyl-1H-pyrrole-2,5-bis(carbothioamide), or to the mixed ligand where only one of the thioamide substituents had converted to a benzothiazole. The essential role of Cu for the ring closure reaction was also established by comparing its complex with structural features of the analogous Co(II) complex, the latter revealing no ring closure to give benzothiazole substituents and co-crystallisation of a mixed Co(II)/Co(III) complex. Finally, the structure and photophysical properties of the corresponding 3,4-diphenyl-2,5-bis(benzothiozol-5-yl)-pyrrole ligand, obtained via treatment of the thioamide with K3[Fe(CN)6], were also investigated revealing a blue-centered emission.

Graphical abstract: Further insight into the coordination of 2,5-dicarbothioamidopyrroles: the case of Cu and Co complexes

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Publication details

The article was received on 16 Mar 2011, accepted on 04 May 2011 and first published on 07 Jul 2011


Article type: Paper
DOI: 10.1039/C1DT10441A
Dalton Trans., 2011,40, 12097-12105

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    Further insight into the coordination of 2,5-dicarbothioamidopyrroles: the case of Cu and Co complexes

    L. E. Karagiannidis, P. A. Gale, M. E. Light, M. Massi and M. I. Ogden, Dalton Trans., 2011, 40, 12097
    DOI: 10.1039/C1DT10441A

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