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.