Preparations Of Mono-Amine Chiral And Multi-Amine Symmetric Schiff-Base Compounds For Syntheses And Structures Of Their Ruthenium Complexes

Syntheses, structures and properties of a series of ruthenium complexes containing mono-amine chiral asymmetry Schiff-base and multi-amine symmetric guanidine Schiff base ligands were reported in this thesis. A new series of Schiff base ligands were synthesized from novel amines and varieties of salicylaldehyde derivatives by condensation reaction. Coordination modes of ligands form a schiff base ruthenium complex was studied, which are different from conventional Schiff base. Initially, four common ruthenium starting materials were synthesized from RuCl₃�xH₂O; 24 kinds of chiral asymmetry Schiff base?L1^*H-L24^*H? and 40 species guanidine Schiff base ligands?DG1-DG20-NH�HCl, TG1-TG20-N�HCl? were prepared from several kinds of aldehydes?salicylaldehydes dominated? with a chiral amine, 1,3-diamino guanidine hydrochloride, triaminoguanidine hydrochloride, respectively. Exploring the solubility and crystallization conditions of the ligands, Crystal structures of seven kinds of mono-amine chiral asymmetry Schiff base ligands?L4^*H, L5^*H, L7^*H, L9^*H, L11^*H, L20^*H and L23^*H? and nine kinds of multi-amine symmetric guanidine Schiff base ligands?DGx-NH�HCl, x=3?6?9?16 and 18; TGx-N�HCl, x=6, 10, 14 and 18? were gained by evaporation diffusion method ultimately. X-ray single crystal diffraction analyzes their structural properties, the chiral mono-amine asymmetrical Schiff base ligands were characterized by means of NMR, IR, UV-Vis and FS additionally. Interaction of two kinds of chiral Schiff base ligand L4^*H, L6^*H with an equimolecular ratio of [RuCl₂?PPh₃?₃], [Et₄N][RuCl₄?CH₃CN?₂], [RuCl₃?NO??PPh₃?₂] ruthenium starting material in THF, deprotonating with triethylamine and stirring 8 h at reflux, three kinds of asymmetric chiral Schiff base ruthenium metal complexes [Ru?PPh₃?Cl?L4^*?₂]?1?, [Et₄N][RuCl₂?L6^*?₂]?2? and [RuCl₂?NO??PPh₃??L6^*?]?3? were obtained. Single crystal structure analysis showed that complexes 1-3 are Ru?II? and Ru?III? species. N,O atoms participate in coordination to ruthenium centre forming a six-membered ring in complexes 1-3, which all showed six-coordinated octahedral structure. Complexes 1 and 2 contain two molecule Schiff base ligands, while complex 3 contains one. In addition, complexes 1-3 were characterized by IR, UV-Vis and FS spectrum. Treatment of DG1-NH�HCl, DG4-NH�HCl, DG19-NH�HCl multi-amine symmetric guanidine Schiff base with equal equivalent of [RuHCl?CO??PPh₃?₃] in the presence of triethylamine and tetrahydrofuran?THF? as a solvent was heated to reflux. With standard Schlenk techniques, three mononuclear ruthenium Schiff base metal complexes [RuH?CO??PPh₃?₂?DG1-NH₂?]?4?, [RuH?CO??PPh₃?₂?DG4-NH₂?]?5? and [RuH?CO??PPh₃?₂?DG19-NH₂?]?6? were isolated as yellow bulk crystals. Molecular structural determination through single crystal X-ray diffraction measurement displayed that Ru?II? metal centres coordinated with N,N atoms to form a rare four-membered ring, which are different from common N,O atoms, but they are still six-coordinated to form octahedral configuration, they were also characterized by IR and NMR spectrum.