Organometallic Ruthenium Complexes Containing Dithionaphthoate Ligands

Transition metal-sulfur complexes are of great significance due to their diverse bonding possibilities and important roles in bioinorganic chemistry and homogeneous catalysis.In recent years,there has been an increasing interest in ruthenium complexes with electron-rich sulfur ligands,in part because of the high catalytic activity of RuS₂ in various types of hydrotreating processes.A series of mononuclear organoruthenium complexes containing bidentate sulfur-donor ligands have been designed and successfully prepared in this thesis.The Grignard reagents were prepared by using accordingα-bromonaphthalene,β-bromonaphthalene and 1,4-bromonaphthalene,which were further reacted with carbon disulfide in tetrahydrofuran to obtain the ligands[（Et₄N）(α-C₁₀H₇CS₂)]（L1）,[（Et₄N）,(β-C₁₀H₇CS₂)]（L2）and[（Et₄N）(S₂CC₁₀H₆CS₂)（Et₄N）]（L3）,respectively.Interaction of these ligands with[Ru（CO）₂Cl₂]_n,[Ru（COD）Cl₂]_n,[Ru（bpy）₂Cl₂?2H₂O]or other organoruthenium startings in refluxing tetrahydrofuran afforded the ruthenium complexes[Ru（CO）₂(α-C₁₀H₇CS₂)₂]（1）、[Ru（COD）(α-C₁₀H₇CS₂)₂]（2）,[（η⁶-p-cymene）RuCl(α-C₁₀H₇CS₂)]（3）,[（η⁶-C₆H₆）RuCl(α-C₁₀H₇CS₂)]（4）,[Ru（PPh₃）₂(α-C₁₀H₇CS₂)₂]（5）,[RuH（CO）（PPh₃）₂(α-C₁₀H₇CS₂)]（6）,[Ru（NO）(α-C₁₀H₇CS₂)₂Cl]（7）,[Ru（bpy）₂(α-C₁₀H₇CS₂)]Cl（8）,[Ru（phen）₂(α-C₁₀H₇CS₂)]Cl（9）,[Ru（CO）₂(β-C₁₀H₇CS₂)₂]（10）,[Ru（COD）(β-C₁₀H₇CS₂)₂]（11）,[RuH（CO）（PPh₃）₂(β-C₁₀H₇CS₂)]（12）,[(S₂CC₁₀H₆CS₂)Ru（CO）₂]_n（13）,[（COD）Ru(S₂CC₁₀H₆CS₂)]_n（14）,[（bpy）₂Ru(S₂CC₁₀H₆CS₂)Ru（bpy）₂]（15）and[（phen）₂Ru(S₂CC₁₀H₆CS₂)Ru（phen）₂]（16）,respectively.The molecular structures of L3,1,2,3,6,8 and 11 have been determined by single-crystal X-ray diffraction.The central ruthenium atoms in these complexes are bonded in octahedral geometry and coordinated with the naphthalene acid ligands with small bite S-Ru-S angles,forming aκ²-S,S-coordination mode.These organoruthenium complexes containing bidentate sulfur-donor ligands were characterized by nuclear magnetic resonance（NMR）,infrared（IR）and ultraviolet（UV-vis）spectroscopies,and their electrochemical properties were also investigated.