Study On The Synthesis And Reactivities Of Substituted Tetramethylcyclopentadienyl And Indenyl Metal Carbonyl Compounds

Increasing attention has been paid to cyclopentadienyl or indenyl ligands metalcomplexes whose side chain contains heteroatoms. The N atom has a strong ability ofcoordination with transition metal because of their lone electron pair, the Br atom has a strongability of departure that can promote the connection of metal atoms and carbon atoms that notonly produced more novel metal carbonyl compounds in the structure and properties, greatlyenriched the kinds and numbers of carbonyl metal complexes, but also provided morepractical value and theoretical basis in the catalytic performance of metal carbonylcompounds in organic reactions. It has potential application prospect. In this dissertation,reactions of two substituted tetramethylcyclopentadienyl ligands [C5Me4HR][R=PhBr-4(1),(MeC5H3N)CH2(2)] with Ru3(CO)12, Fe(CO)5, Mo(CO)6were studied, six new complexeswere obtained; meanwhile reactions of pyridyl-substituted indenyl ligand with Ru3(CO)12afforded a novel pyridyl-substituted indenyl trinuclear ruthenium complex, investigated itsreactivity and obtained six new complexes. Ten complexes of them were characterized by X-ray diffraction and their structures were also discussed. The main results are listed asfollowing:(1) In this thesis, two substituted tetramethylcyclopentadienyl ligands [C5Me4HR][R=PhBr-4(1),(MeC5H3N)CH2(2)] were synthesized. Reactions of the two ligands withRu3(CO)12, Fe(CO)5and Mo(CO)6in refluxing xylene gave the corresponding dinuclear metalcarbonyl complexes trans-{[η5-C5Me4C6H4-4-Br]Ru(CO)(μ-CO)}2(3), trans-{[η5-C5Me4C6H4-4-Br]Fe(CO)(μ-CO)}2(4), trans-[η5-C5Me4C6H4-4-Br]2Mo2(CO)6(5), trans-{[η5-(MeC5H3N)CH2C5Me4]Ru(CO)(μ-CO)}2(6), trans-{[η5-(MeC5H3N)CH2C5Me4]Fe(CO)(μ-CO)}2(7), trans-[η5-(MeC5H3N) CH2C5Me4]2Mo2(CO)6(8) respectively. The crystalstructures of complexes3,5,6and7were obtained by X-ray. The crystal structures show that:the heteroatoms of side chains had important effect on the M-M bond distances of thecomplexes by its electronic effect and steric effect.(2) Pyridyl substituted indenyl ligand1-(6-bromo-2-pyridyl)indene (9) was synthesized.Reaction of the ligand with Ru3(CO)12in refluxing heptane gave the corresponding trinuclearruthenium complex {μ2-5:1-(C5H3N-6-Br)(C9H5)}Ru3(CO)9(10) whose C-H bond wasactivated. The reactivities of complex10were studied: reaction of complex10with ligand9obtained {5-(C5H3N-6-Br)(C9H5)}{1-(C5H3N)(C9H6)}Ru2(CO)4(11) and ligand mutualcoupling product12; the reaction of complex10in refluxing toluene obtained {μ3-6:3:1- (C5H3N-6-Br)(C9H5)}Ru3(CO)7(13); the reaction of complex10with indene obtained [{(5-C9H7)Ru(CO)2}2](14); the reaction of complex10with fluorene obtained {μ3-6:3:1-(C5H3N-6-Br)(C9H5)}Ru3(CO)7(13), in which the fluorine was not involved in the reaction,indicated the fluorine has a low capacity of reaction; the reaction of complex10withphenylethylene or divinylbenzene obtained {(5-(C5H3N-6-Br)(C9H5CHCH2Ph}Ru2(CO)5(15)and {(5-(C5H3N-6-Br)(C9H5CHCH2PhCHCH2}Ru2(CO)5(16), an alternative mechanism forthe formation of dinuclear ruthenium complexes via the insertion of alkenes into the Ru-C(η1)bond is proposed. The crystal structures of complexes11,12,13,14and15were determinedby X-ray. The results above illustrated that: indene has the ability of coordination withtransition metal ruthenium, N atom of the pyridine can also coordinate with ruthenium, so anovel trinclear metal carbonyl complex10was obtained. Its reactivities with pyridinederivatives, obtained one unrespected metal carbonyl complexe; reaction of10in refluxingtoluene afforded an unexpected complex, via the loss of two CO and the coordinationbetween benzene with Ru; reaction of10with indene afforded a trans Ru-Ru binuclearcarbonyl complexes which has higher thermal stability; its reactivities with terminal alkenesafforded unrespected binuclear carbonyl complexes that via insertion of alkenes into the Ru-C(η1) bond.