This thesis describes the synthesis and characterization of a new class of Ru-vinylidens which contain both sp hybridized C-Ru and sp3 hybridized C-Ru bonds. Multinuclear NMR as well as LC-MS spectroscopy methods have been used to analyze and confirm the structures, with the overall aim to synthesize Ru-vinylidenes from internal alkynes and study their electrochemical behavior.
Chapter 1 gives an introduction and summary of the known organoruthenium chemistry with focus on the vinylidenes reported to date. Chapter 2 reports experimental procedures for synthesis of ruthenium precursors [PPN]2 [Ru(EDTA)].xH2O, [PPN]2[Ru(HNTA) 2], CpRu(PPh3)2Cl and [CpRu(PPh3) 2]BArF4. Electrochemical studies have been performed on the complex [CpRu(PPh3)2(=C=C(Ph)(C(O)Ph)]BAr F4 (Compound 6). Electrochemistry shows that ruthenium vinylidene [CpRu(PPh3)2(=C=C(Ph)(C(O)Ph)]BAr F4 undergoes into a reduction to make an anionic Ru vinylidene species [CpRu(PPh3) (=C=C(Ph)(C(O)Ph)]- which is expected to be a strong nucleophile and would attack electrophiles such as MeI or halogenated solvents. Chapter 3 discusses synthetic approaches as well as full characterization of the prepared complexes by spectroscopic methods. Chapter 4 describes electrochemistry of the parent [CpRu(PPh 3)2(=C=C(Ph)(C(O)Ph))]BArF4 vinylidene complexes which undergoes an ECE set of reductions to generate anionic [CpRu(PPh 3)(=C=C(Ph)(C(O)Ph)]- intermediate.
CH2[CpRu(=C=C(Ph)(C(O)Ph)(PPh3)]2 is presumably formed when cyclic voltammetry is performed in dichloromethane media. Noteworthy, this novel class of vinylidenes is synthetically significant and might be useful as catalyst in organic synthesis. Conclusions and future works of the project are discussed in Chapter 5. The appendix provides spectra of the complexes, LC-MS figures and selected CV data.
|Advisor:||Shaw, Michael J.|
|Commitee:||Dixon, Robert P., Jones, Myron W., Khazaeli, Sadegh, Voss, Eric J.|
|School:||Southern Illinois University at Edwardsville|
|School Location:||United States -- Illinois|
|Source:||MAI 52/02M(E), Masters Abstracts International|
|Keywords:||Cyclic voltamettry, Ece mechanism, Organometallic chemistry, Ruthenium, Vinylidenes|
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