Studies On Synthesis,Structures And Properties Of Half-sandwich Iridium,Rhodium And Ruthenium Complexes

In the past few decades,the late transition metal ruthenium,rhodium and iridium complexes with a half-sandwich structure have been extensively explored by scientists,and occupied an important part in organometallic chemistry.The literature reports on organometallic complexes with half-sandwich structures are also emerging in endlessly.This thesis focuses on the half-sandwich organometallic complexes.Base on[Cp*MCl₂]₂?Cp*=?⁵-C₅Me₅,M=Ir or Rh?or[?p-cymene?RuCl₂]₂ units,coordinated with organic ligand,synthesis mononuclear,binuclear,and supramolecular coordination complexes,and then explored the properties of the complexes.?1?Through metal-mediated C-H bond activation,treatments of dimeric metal complex[Cp*IrCl₂]₂ with a serious of different substituents Schiff base ligands,afforded the corresponding C,N-chelate mononuclear half-sandwich complexes.These Ir-based complexes exhibit high catalytic activity for norbornene polymerization(2.72×10⁶ g PNB mol^–1 Ir h^–1).Both steric and electronic effects of the substituted groups have influences on the behaviors of the polymerization processes.?2?Based on[Cp*MCl₂]₂?M=Ir or Rh?units,we synthesized a series of binuclear half-sandwich[Cp*M?N^N?]?M=Ir,Rh?complexes coordination with pyrrolyl-azine ligands.Those complexes as catalysts for water oxidation with double-site,and they exhibit high catalytic activity(TOF=0.8 s^-1)and low overpotential?325 mV?.?3?Based on a dinuclear Ru complex with the metal-metal distance of 12.840?6????,two types of Ru supramolecular coordination complexes were obtained via self-assembly.The coordination-driven self-assembly complexes with tunable host cavity can encapsulate one or two guests smoothly throughp-p*interaction.