Synthesis And Characterization Of O-Aminobenzenethiolate-Bri-Dged Di/multinuclear Ruthenium Complexes

In this thesis,based on strategy of bimetallic cooperation effect,we adopt the redox non-innocent o-aminobenzenethiol?abt?ligand and utilize central metal exchange method to construct abt-bridged diruthenium complexes and study their rich reactivities.First,by metathesis reaction between methoxy bridged diruthenium precursor complex[Cp*Ru??-OMe?₂RuCp*]?Cp*=?⁵-C₅Me₅?and Na₂abt,abt-bridged diruthenium complex[Cp*Ru??-?²:?⁴-abt?RuCp*]?1?was successfully obtained.X-ray single-crystal diffraction experiment shows that one double bond in aromatic ring of the abt ligand binds on one ruthenium centre in a side-on fashion to form stable dinuclear framework.In addition,due to the unique coordination mode of the abt ligand,the other ruthenium centre is in coordinatively unsaturated.Therefore,this complex can be regarded as a potential functional mimic of metalloenzymes.Secondly,studies on the oxidation reaction of complex 1 was carried out.In the presence of one-electron oxidant Fc·PF₆,Ru^IIRu^III complex 1 can not convert into Ru^IIRu^IIIII one-electron oxidative product,however,the C-H bond activation of methyl group in Cp*ligand induced by the ruthenium centre led to afford a more stable Ru^IIIRu^IIIII fulvene-like complex[??⁵:?¹-C₅Me₄CH₂?Ru??-?²:?⁴-abt?RuCp*][PF₆]?2?.This system provided a new idea for inert C-H bond activation by bimetallic cooperation.Thirdly,investigations on the protonation of complex 1 was performed.Treatment of complex 1 with HBF₄·Et₂O undergone oxidative addition to generate a diruthenium hydride bridged complex[Cp*Ru??-?²:?⁴-abt???-H?RuCp*][BF₄]?3?.X-ray single-crystal diffraction experiment shows that the hydride group was bridged between the two ruthenium centers in?-?²:?⁴ fashion to form a stable three-centre two-electrons bond,moreover,the abt ligand still bind to one ruthenium centre in a?-?²:?⁴ pattern,which causes the formation of asymmetric binuclear structure.Finally,using different ruthenium reaction precursors,coordinatively saturated binuclear complex[Cp*Ru??-?¹:?²-abt?]₂?4?and tetranuclear complex 5 were synthesized.Besides,redox properties of di/multinuclear ruthenium complexes were explored by the cyclic voltammetry.