Chloro-lanthanide, and plutonium complexes containing the hydrotris (3,5-dimethylpyrazol-1-yl)borate ligand: the crystal and molecular structures of [PrCl (μ-Cl) TpMe2 (3,5-Me2pzH)]2 and YbCl 2TpMe2 (THF)

Abstract

Reactions of PuCl 3 and LnCl 3 (Ln=Pr, Nd ) with the stoichiometric amount of KTp Me2 (Tp Me2=HB (3,5-Me 2pz) 3) yielded the dimeric [MCl ( μ-Cl)Tp Me2 (Me 2pzH)] 2 compounds (M=Pu (1), Pr (2), Nd (3)). The analogous reaction with YbCl 3 afforded the monomeric YbCl 2Tp Me2 (THF) complex (4). The crystal and molecular structures of 2 and 4 have been assessed by means of single crystal X-ray diffraction analysis. In 2 each Pr atom is seven-coordinate and is linked to the adjacent metal centre by two bridging chlorine ligands. In 4 the Yb atom is six-coordinate and displays octahedral geometry. 4 undergoes intermolecular rearrangement reactions to yield [YbCl 2TP Me2 (Me 2pzH)]·THF (6) and [YbCl 3Tp Me2] − [ (Me 2pzH 2)] + (7). The molecular structures of 6 and 7 were determined by X-ray diffraction. In 6 the tridentate ligand, the two chlorine atoms and the nitrogen atom of the neutral dimethylpyrazole describe a distorted octahedron. 7 consist of discrete [YbCl 3Tp Me2] − and [ (Me 2pzH 2)] + ions, with the ytterbium atom of the cation coordinated to three pyrazolyl nitrogens and three chlorine atoms.