Graduate Thesis Or Dissertation

 

Synthesis of substituted cyclooctatetraenide dianions ; Cycloheptadienyl complexes of the ḏ- and f̲-transistion elements ; Reactions of cyclohexanone with metal vapors Public Deposited

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  • I. Lithium alkyl and aryl monosubstituted cyclooctatetraenide dianions (Li₂ C₈H₇-R; R = methyl, n- butyl, sec- butyl, tert- butyl, phenyl and benzyl) were synthesized by the reaction of the appropriate organolithium reagent with cyclooctatetraene in diethyl ether or tetrahydrofuran. The reaction occurred cleanly and with good yield of lithium monosubstituted cyclooctatetraenide dianion at ambient or lower temperature for all organolithium reagents studied except tert-butyl-lithium. (TMEDA is needed as an activator for methyllithium.) Substituted cyclooctatetraenide dianions were characterized by chemical reactions, i. e., oxidation, hydrolysis and deuterolysis, as well as, preparation of organometallic derivatives, substituted uranocenes. A two step mechanism for the reaction is proposed which involves the addition of the organolithium reagent to cyclooctatetraene followed by proton removal to yield the appropriate ten-Tr electron aromatic dianion. Several other alkyl organometallic compounds failed to produce mono substituted cyclooctatetraenide dianions on reacting with cyclooctatetraene. Lithium hexaalkyluranate(IV) complexes reacted with cyclooctatetraene to give uranocene in good yield along with high yields of coupled alkyl products. II. The addition of lithium cycloheptadienide (LiC₇H₈-R; R = hydrogen, methyl and n-butyl) to lanthanide and actinide chlorides results in the facile formation of unstable cycloheptatrienyl trianionmetal compounds. Characterization of the ten-π aromatic cycloheptatrienyl trianion (C₇H₆-R⁻³) was made by identification of the organic products resulting from chemical reactions of the coordinated ligand, for example, hydrolysis, deuterolysis and oxidation, as well as, spectroscopic characterization (¹H NMR) of paramagnetic uranium(IV) compounds. Qualitative analysis of the paramagnetic ¹H NMR shifts are discussed based on the assumption that metal-ligand bond distances and magnetic properties in cycloheptatrienyl-uranium(IV) compounds are similar to those of uranocene. Formation of the cycloheptatrienyl trianion is believed to occur by the loss of two methylene protons from the metal coordinated cycloheptadienide ion. The role of the lanthanide and acinide metal ions in cycloheptatrienyl trianion formation is discussed. III. Metal atom vapors of several d- and f-transition elements were cocondensed with cyclohexanone at -196°C. Radical reduction of cyclohexanone to bicyclohexy1-1'diol, a pinacol, was observed for elements which are both highly electropositive and form strong metal oxygen bonds, for example, the early transition, lanthanide and actinide elements. High yields of aldol condensation products were produced along with a small amount of bicyclohexylidene. Metal atoms of the latter transition elements were much less reactive with cyclohexanone and did not yield a pinacol product. Titanium clusters were prepared by codepositing titanium atoms with a large excess of solvent. Titanium clusters were less reactive than titanium atoms toward cyclohexanone radical reduction reactions. High surface area titanium powders produced by solution techniques, yield pinacols when cyclohexanone reacts in excess and further deoxygenate pinacolic dianions to olefins under conditions of limited stoichiometry. Nitrobenzene was deoxygenatively coupled to azoxybenzene and azobenzene by lanthanide and actinide metal atoms.
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