Dppz配体10,13-位由芳香基取代的新型单核钌配合物的合成

Synthesis of novel mononuclear Ru(Ⅱ) complexes with 10,13-diaryl substituents on the dppz ligands

目的本论文以1,10-邻菲罗啉(1,10-phenanthroline,phen)为辅助配体,在主配体联吡啶类(3,2-a:2'-3'-c)吩嗪[pyrido-(3,2-a:2',3'-c) phenazine,dppz]的10,13-位分别引入噻吩、苯并噻吩、呋喃及苯并呋喃,设计并合成出对应4种新型单核二-(1,10-邻菲罗啉)-吡啶类(3,2-a:2'-3'-c)吩嗪合钌(Ⅱ)衍生物。方法首先通过Suzuki偶联反应得到4种苯并噻二唑中间体,然后经Co Cl2催化、Na BH4还原得到邻苯二胺类化合物,再经缩合反应得到对应的目标配合物。结果苯并噻二唑中间体及对应的4种目标配合物通过磁共振氢谱、碳谱及高分辨质谱表征,紫外-可见吸收光谱进一步验证了目标配合物结构的正确性。结论本论文通过多步反应合成出以1,10-邻菲罗啉为辅助配体,主配体dppz的10,13-位分别含有噻吩、苯并噻吩、呋喃及苯并呋喃的4种新型单核多吡啶钌配合物。紫外-可见吸收光谱实验表明尽管4种芳香取代基结构有差异,对应苯并噻二唑中间体和钌配合物的吸收光谱相似。

Objective Four new ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10,13-position substituted[pyrido-(3,2-a:2’,3’-c)phenazine,dppz]major ligands including thiophenyl,furanyl,[2-benzo(b)thienyl]-2,1,3-benzothiadiazole and[2-benzo(b)furanyl]-2,1,3-benzothiadiazole will be designed and synthesized.Methods Target complexes were made by condensation reaction of ruthenium complex with the appropriate 3,6-diaryl substituted benzene-1,2-diamine.The latter 3,6-diaryl substituted benzene-1,2-diamine was obtained by a Suzuki-coupling reaction,and subsequently by reduction with Na BH4 under catalysis of Co Cl2.Results Benzothiadiazole intermediates and corresponding target complexes are well characterized by1 H nuclear magnetic resonance(NMR),13 C NMR and TOF-Mass.UV-vis absorption spectra of all ruthenium complexes further verify the structures of the target complexes.Conclusion In this paper,we have synthesized four mononuclear ruthenium complexes with 1,10-phenanthroline ancillary ligand and 10,13-diaryl including thiophenyl,furanyl,[2-benzo(b)thienyl]-2,1,3-benzothiadiazole and[2-benzo(b)furanyl]-2,1,3-benzothiadiazole,substituted dppz as major ligand through multiple steps.Both four 4,7-position substituted 2,1,3-benzothiadiazole intermediates and corresponding ruthenium complexes exhibit substantially similar absorption spectra despite the structural difference.