Chemical Consequences of Assemblage of Transition Metal Ions or Metal Complexes

点击翻译按钮获取中文摘要

1. ^<99>Ru NMR of Ru (III) Dimer and Related Compounds. ^<99>Ru NMR spectra have been measured on senen Ru (III) polynuclear complexes, which are essentially diamagnetic through Ru (III)-Ru (III) interaction. Effects of oxidation sate, donor atom, and metal-metal bond upon chemical shift have been studied.2. Synthesis and Characterization of Carboxylate Bridged Polynuclear Complexes. More than 20 new compounds have been synthesized, and their properties have been studied from the view point of the assemblage effects.(1) Novel Pt (III) dimers in which CH_2COO^<2-> bridges two Pt's through C and O have been synthesized.(2) In a pyrazine bridged dimer of the oxo, carboxylato bridged Ru trinuclear cluster, we produced successfully "mixed valence" states between the trinuclear units.(3) We found that large (20-26) membered Curtis macrocycles (fully saturated form) act as a dinucleating ligand for Cu (II) by taking up two additional small bridging ligands such as OR^-, OH^-, or CH_3COO^-. Such Cu (II) dimers show generally anti-ferromagnetic interaction. The degree of the interaction was found to be very sensitive to the core structure of the dimer.(4) A new photo-induced ligand substitution was found in oxo, carboxylato bridged trinuclear Ru complexes with the CO terminal ligand.3. Synthesis of Macromolecular Complexes having Trinuclear Ru Cluster Unit. Six new macromolecular complexes comprised of 4-polyvinylpyridine and oxo, carboxylato bridged Ru trinuclear cluster have been synthesized. Under certain conditions, thin film of the complex coated on a glassy carbon electrode showed reversible redox response in an aqueous solution.