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Issue 9, 2016
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A novel samarium(II) complex bearing a dianionic bis(phenolate) cyclam ligand: synthesis, structure and electron-transfer reactions

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Abstract

The reaction of the hexadentate dianionic 1,4,8,11-tetraazacyclotetradecane-based bis(phenolate) ligand, (tBu2ArO)2Me2-cyclam2−, with [SmI2(thf)2] in thf resulted in the formation of the divalent samarium complex [Sm(κ6-{(tBu2ArO)2Me2-cyclam})] (1). X-ray diffraction studies revealed that after recrystallization from n-hexane/thf complex 1 has a monomeric structure and does not contain thf molecules coordinated to the Sm(II) center. However, UV-vis and 1H NMR spectroscopy of 1 evidenced the formation of thf-solvated complexes in neat thf. Reductive studies show that complex 1 can act as a single electron-transfer reagent and form well-defined Sm(III) species. The reaction of 1 with several substrates, namely, TlBPh4, pyridine N-oxide, OPPh3, SPPh3 and bipyridines, are reported. Spectroscopy studies, including NMR, and single crystal X-ray diffraction data are in agreement with the formation of cationic Sm(III) species, monochalcogenide bridged Sm(III) complexes and Sm(III) complexes with bipyridine radical ligand, respectively.

Graphical abstract: A novel samarium(ii) complex bearing a dianionic bis(phenolate) cyclam ligand: synthesis, structure and electron-transfer reactions

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Publication details

The article was received on 26 Nov 2015, accepted on 14 Jan 2016 and first published on 14 Jan 2016


Article type: Paper
DOI: 10.1039/C5DT04647E
Citation: Dalton Trans., 2016,45, 3778-3790
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    A novel samarium(II) complex bearing a dianionic bis(phenolate) cyclam ligand: synthesis, structure and electron-transfer reactions

    L. Maria, M. Soares, I. C. Santos, V. R. Sousa, E. Mora, J. Marçalo and K. V. Luzyanin, Dalton Trans., 2016, 45, 3778
    DOI: 10.1039/C5DT04647E

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