Half-sandwich Organometallic Ruthenium, Iridium, Rhodium Macrocyclic Compounds Synthesized And Its Nature

Multinuclear rectangles and cages based on organometallic Ru, Co, Ir, Rh and Re complexes have been studied extensively by many groups, as there are three available coordination sites of (arene)-Ru, CpCo, Cp*M (M=Rh, Ir) or Re(CO)3 complexes that can be used to construct metallamacrocyclic complexes as well as coordination cages, some of which show special ability in ion affinity and selectivity.Oxamide type compounds comprise a very interesting family in coordination chemistry, as they can chelate as well as bridge the metal ions to construct discrete and extended structures via the cis or trans conformation. This thesis described the stepwise formation of bi-and tetra-nuclear half-sandwich ruthenium complexes bearing oxamidato bridges, based on pyridyl subunits.1.Molecular rectangles of half-Sandwich p-cymene ruthenium complexes bearing oxamidato ligands.A series of binuclear half-sandwich p-cymene ruthenium complexes bearing oxamidato ligands was synthesized by the reactions of the lithium salts of oxamide with [(p-cymene)RuCl2]2, respectively. Treatment of the binuclear complexes with bidentate ligands such as 4,4'-bipyridine (4,4'-bpy) and trans-1,2-bis(4-pyridyl)ethylene (bpe) in the presence of AgOTf (OTf=CF3SO3) gave the corresponding tetra-nuclear complexes in high yields. All compounds have been characterized by NMR and IR spectra and elemental analyses.2.[2+2] photodimerization in solid state:aided by molecular templates of rectangular macrocycles bearing oxamidato ligands.A series of binuclear half-sandwich iridium and rhodium complexes bearing oxamidato ligands functioned as potential "organometallic clip" liner templates was synthesized by the reactions of the lithium salts of oxamide with [Cp*MCl2]2 (M=Ir or Rh), respectively. Treatments of the binuclear complexes with trans-1,2-bis(4-pyridyl)ethylene (4,4'-bpe) in the presence of AgOTf (OTf=CF3SO3) gave the corresponding tetra-nuclear complexes in high yields. Confirmed by the single-crystal X-ray analysis, the molecular structures of tetra-nuclear complexes showed that the twoμ-4,4'-bpe ligands are close to each other within 4.2 A to allow the [2+2] photoreaction in solid state.