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



Maria, Leonor, Soares, Marina, Santos, Isabel C, Sousa, Vania R, Mora, Elsa, Marcalo, Joaquim and Luzyanin, Konstantin V ORCID: 0000-0001-9312-7139
(2016) A novel samarium(II) complex bearing a dianionic bis(phenolate) cyclam ligand: synthesis, structure and electron-transfer reactions. DALTON TRANSACTIONS, 45 (9). pp. 3778-3790.

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Abstract

The reaction of the hexadentate dianionic 1,4,8,11-tetraazacyclotetradecane-based bis(phenolate) ligand, (tBu2ArO)2Me2-cyclam(2-), with [SmI2(thf )2] in thf resulted in the formation of the divalent samarium complex [Sm(κ(6)-{(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 (1)H 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 electrontransfer 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.

Item Type: Article
Uncontrolled Keywords: Biotechnology
Depositing User: Symplectic Admin
Date Deposited: 19 Aug 2016 08:37
Last Modified: 15 Mar 2024 05:09
DOI: 10.1039/c5dt04647e
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URI: https://livrepository.liverpool.ac.uk/id/eprint/3002977