Studies On Synthesis And Structure Characterization Of Indenyl Alkyne Carbonyl Cobalt Cluster And Alkyne Cycloaddition Reactivity

Indenyl group with similar chemical properties to cyclopentidienyl and phenyl unitscan coordinate in η5bonding mode with many transition metals to form sandwich orhalf-sandwich type organometallic compounds. Additionally, indenyl group can alsocoordinate with almost all metals in η1、η3、η6modes to form σ-or π-type organometalliccompounds. The rich bonding patterns with transition metals of indenyl ligand have raisedgreat interest and motivated the development both experimental and theoretic studies oforganometallic chemistry. In1983, Basolo and coworkers observed that replacement of acyclopentadienyl ring (C-5H5) by an indenyl unit (C9H-7) led to strongly acceleratedsubstitute reaction rate. Based on this phenomenon, the concept of “indenyl effect” wasraised by Basolo.The carbonyl cobalt clusters as catalyst precursors play an important role in the [2+2+2] alkyne cycloaddition reaction, and have been widely used in the preparation of varioussubstituted benzene derivatives. In this dissertation, new indenyl-alkyne carbonyl cobaltclusters were designed and synthesized by using indenyl-alkyne as raw materials. Usingindenyl-alkyne carbonyl cobalt clusters as the catalyst precursors, the ferrocenyl indenylsubstituted benzene derivatives were successfully obtained by [2+2+2] cycloadditionreaction of ferrocenylacetylene with indenyl-alkyne. The indenyl-alkyne carbonyl cobaltclusters will be widely used in catalytic reactions, and ferrocenyl indenyl substitutedbenzene derivatives will play an important role in electrochemistry research and moleculardesign of special complexes.The main works in the dissertation are as follows:1． Using2-Bromoindanone and trimethylsilylacetylene as raw material,2-trimethylsilylethynyl indene (IndC≡CSiMe3) was synthesized through Sonogashiracoupling reaction; Under weakly alkaline condition,2–indenylacetylene IndC≡CH wasprepared by hydrolysis reaction of2-trimethylsilylethynyl indene (IndC≡CSiMe3).Ferrocenylacetylene (FcC≡CH) was synthesized by elimination reaction of chloroacroleinin NaOH.2. A new indenyl-alkyne carbonyl cobalt cluster [IndC≡CSiMe3(Co2CO6)](1) wassynthesized by the coordinated reaction of2-(trimethylsilyl ethynyl) indene withoctacarbonyl dicobalt using cyclohexane as the solvent.3. A new indenylacetylene carbonyl cobalt cluster [IndC≡CH(Co2CO6)](2) was synthesized by the coordinated reaction of2-indenylacetylene with octacarbonyl dicobaltusing cyclohexane as the solvent.4. Hexaphenylbenzene [C6(C6H5)6](3) was synthesized by [2+2+2]diphenylacetylene cycloaddition reaction using cluster1as catalyst precursor and dioxaneas the solvent.5. The new ferrocenyl indenyl substituted benzene derivatives [[Ind(Fc)2SiMe3]C6H2](4) and [[Ind(Fc)2SiMe3]C6H2](5) were synthesized by [2+2+2] ferrocenylacetylenecycloaddition reaction using cluster1as catalyst precursor and dioxane as the solvent. Thecompound4，5are a couple of isomers. Their structure may be1-indenyl-2,4-diferrocenyl-6-trimethylsilylbenzene,1-indenyl-3,5-diferrocenyl-6-trimethylsilylbenzene and1-indenyl-3,4-diferrocenyl-6-trimethylsilylbenzene.The ligand2-trimethylsilylethynyl indene wasreacted, and the carbonyl cobalt cluster core from catalyst precursor (cluster1) acted as acatalyst in this cycloaddition reaction.6. The new ferrocenyl indenyl substituted benzene derivatives [[Ind(Fc)2]C6H3](6)and [[Ind(Fc)2]C6H3](7) were synthesized by [2+2+2] ferrocenylacetylene cycloadditionreaction using cluster2as catalyst precursor and dioxane as the solvent. The compound6，7are a couple of isomers. Their structure may be1-indenyl-2,4-diferrocenylbenzene,1-indenyl-3,5-diferrocenylbenzene and1-indenyl-3,4-diferrocenylbenzene. The ligand2-indenylacetylene was reacted, and the carbonyl cobalt cluster core from catalystprecursor (cluster2) acted as a catalyst in this cycloaddition reaction.7. The component and molecular structure of compounds1-7were characterized byFTIR，UV-Vis,1H NMR，13C NMR, MS, HPLC-MS and Element Analysis techniques.8. The single crystals of cluster1were successfully obtained by columnchromatography and recrystallization method, and the molecule and crystal structures ofcluster1were determined through X-ray single crystal diffractometer techniques.