| Abstract |
The reaction of the hexadentate dianionic 4,8,11-tetraazacyclotetradecane-based bis(phenolate) ligand, ((BArO)-Ar-u2)(2)Me-2-cyclam(2-) with [SmI2(thf)(2)] in thf resulted in the formation of the divalent samarium complex [Sm(kappa(6)-\((ArO)-Ar-tBu)(2)Me-2-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 I-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 electron transfer reagent and form well-defined Sm(iu) species. The reaction of 1 with several substrates, namely, TEI3Ph2, pyridine N -oxide, OPPh3, SPPh3 and bipyridines, are reported. Spectroscopy NMR, and single crystal X-ray diffraction data are in agreement with the formation species, monochalcogenide bridged Sm(iii) complexes and Sm(ui) complexes with bipyridine radical ligand, respectively. |
