Chloro-lanthanide, and plutonium complexes containing the hydrotris(3,5-dimethylpyrazol-l-yl)borate ligand: the crystal and molecular structures of [PrCl(#mu#-Cl)Tp~(Me_2) (3,5-Me_2pzH)]_2 and YbCl_2TP~(Me2) (THF)

摘要

Reactions of PuCl_3 and LnCl_3 (Ln = Pr, Nd) with the stoichiometric amount of KTp~(Me_2) (Tp~(Me_2) = HB(3,5-Me_2pz)_3) yielded the dimeric [MCl(#mu#-Cl)Tp~(Me_2)(Me_2pzH)]_2 compounds (M = Pu (1), Pr (2), Nd (3)). The analogous reaction with YbCl_3 afforded the monomeric YbCl_2TP~(Me_2)(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~(Me_2)(Me_2pzH)] centre dot THF (6) and [YbCl_3Tp~(Me_2)]~-[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~(Me_2)]~- and [(Me_2pzH_2)]~+ ions, with the ytterbium atom of the cation coordinated to three pyrazolyl nitrogens and three chlorine atoms.