The synthesis of the anionic organolanthanide complexes supported by H 2bppda (H 2bppda = N,N′-bis(2-pyrrylmethylidene)-1,2- phenylenediamine) ligand via different synthetic strategies is reported. Treatment of 1:4 mixture of LnCl 3(THF) 3 and LiN(SiMe 3) 2 with 2 equivalents of H 2bppda in THF gave complexes of the formula [Li(THF) 4][Ln(bppda) 2]·THF (Ln = Nd (1·THF), Sm (2·THF), Gd (3·THF), Dy (4·THF), Er (5·THF)) and [Li(THF) 5][Yb(bppda) 2] (6). Reaction of Nd(BH 4) 3(THF) 3 with 2 equivalents of Na 2bppda in THF generated [Na(THF) 6][Nd(bppda) 2] (7) in good yield. Treatment of 1·THF with 1 equivalent of CoCp 2 in THF led to the isolation of [CoCp 2][Nd(bppda) 2] (8). All of the complexes have been characterized by single crystal X-ray diffraction and elemental analyses. Complexes 1·THF-5·THF are isomorphous and isostructural, and the geometry of the octa-coordinated Ln 3+ ion in [Ln(bppda) 2] - unit in these complexes is well described as either distorted dodecahedron or distorted bicapped trigonal prism. Lanthanide contraction was observed in 1·THF-5·THF and 6. The structures of complexes 1·THF, 7 and 8 are different from each other due to the variation of the cationic ions. The ring-opening polymerization reaction of -caprolactone initiated by 1·THF was conducted; it showed good activity.
- Crystal structure
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry