Physical Sciences and Mathematics Commons^™

Reductive Cleavage Of Cyclopentadienylmanganese Tricarbonyl, Mani S. Iyer

Masters Theses

Since the isolation of ferrocene in 1951, it has been shown to behave like benzene and may be acylated, sulfonated, metalated, and arylated. Like benzene, it also resists hydrogenation.

Daniel Trifan and Louis Nicholas (1957) were the first to show that ferrocene can be smoothly degraded by lithium and ethylamine. The isolation of free cyclopentadienyl ion on hydrolysis of the reaction mixture indicates that the cleavage leads initially to cyclopentadienyl lithium salt. A similar procedure applied to cyclopentadienylmanganese tricarbonyl also resulted in the formation of cyclopentadienyl lithium salt. This, when added to ferrous chloride, gave ferrocene. This technique can be …

Selected Studies On Certain Iron Sandwich Complexes, Mashitah M. Yusoff

Masters Theses

In these studies, the synthesis of [2.3](1,3)cyclopentadiendoparacyclophane was attempted. Like ferrocene and [2.2]paracyclophane, it is expected to exhibit transannular π-electronic interaction throughout its molecular structure and therefore, one dimensional semiconductivity.

The preparation of dialkylferrocenes had resulted in complex inseparable mixtures. Due to the fluxional nature of its intermediates, their conversion to stable Diels-Alder adducts would facilitate analysis. In this project, certain Diels-Alder adducts of bis-cyclopentadienyliron dicarbonyl intermediates were prepared for analysis.

Very few transition metal complexes of pyrrole are currently known. [2.2](2,5)Pyrroloparacyclophane was perceived to be stable especially as a part of an iron sandwich complex. The final phase …

Micellar Catalysis Of Hydrolysis Of Substituted Hydroxamic Acids With Perfluorooctanoic Acid, Zhongyuan He

Masters Theses

The work demonstrated the effects of differently located and substituted phenyl groups, as well as aliphatic groups in the hydroxamic acids, on micellar catalysis with perfluorooctanoic acid as the reactive counterion surfactant in aqueous acetonitrile solution.

Kinetic rate constant-surfactant concentration profiles for the decano-, 2,5-dimethylphenylaceto-, 4-isopropylphenylaceto-, 4-phenylbutano-, and 6-phenyl-hexanohydroxamic acids were examined and analysis on the data obtained were reported.

The pseudo-phase ion exchange (PPIE) model has been satisfactorily applied to explain the observed micellar effects.

Further investigation into more appropriately substituted hydroxamic acids is suggested in order to obtain a more complete set of data and further evaluation.

Reactivities Of Some Aromatic Compounds At Supercritical Water Conditions, Chun-Cheng Tsao

Masters Theses

The goals of this study are the removal of nitrogen from the extraction products of coal by Supercritical Water and the development of an understanding of the reactions leading to this removal. Six model compounds with structures similar to the intermediates of the coal liquefaction processes were studied. Benzylamine generated toluene through hydrogen abstraction after the C-N bond rupture. To a lesser extent, the oxidation of the benzylic carbon took place leading to benzene formation. Both reaction pathways occurred with equal probability for benzylidenebenzylamine, producing comparable yields of benzene and toluene. Benzaldehyde generated benzene through the oxidation/decarboxylation sequence. Benzyl alcohol …

An Analysis Of Dissolved Organic Compounds And Their Contribution To Iron Complexation In The Shallow Leachate Plume Of The West Kl Landfill Kalamazoo, Michigan, Eric Fahle

Masters Theses

High concentrations of dissolved iron are present in downgradient groundwater samples adjacent to the western border of the West KL Landfill. Analysis by Rudder (1988) of groundwater samples indicates oversaturation of selected iron oxides, iron sulfides and siderite in monitoring wells TW-4 and M3.

Previous research suggests that pyrogallol, gallic acid, tannic acid and similar organic compounds may retard the oxidation of ferrous iron in the shallow leachate plume of the West KL landfill (Rudder, 1988). Present research utilizing solid phase extraction, reverse phase high performance chromatography, Fourier transform IR spectrophotometry, UV/Visible spectrophotometry, and gas chromatography/mass spectroscopy indicate that pyrogallol, …

Development Of Ruthenium Vinylbipyridine Modified Electrode Surfaces For Use In Chemiluminescence-Based Detection Systems, Matthew F. Piescinski

Masters Theses

Based upon the chemiluminescent properties of [Ru(bpy)₃]²⁺ and the proven analytical applications of that complex in the detection of easily reduced anions in solution, a chromatographic detection system was designed utilizing an immobilized form of the Ru(ll) complex. The objective was to create, by electropolymerization, a regenerative chemiluminescent surface on a working electrode. Reductive electropolymerization was accomplished by the use of a [Ru(bpy)₃]²⁺ analog containing the ligand vinylbipyridine. Two analogs, [Ru(vbpy)₃][PF₆]₂ and [Ru(phen)₂(vbpy)][PF₆]₂ were polymerized on platinum, glassy carbon and indium-doped tin oxide working …