The photochemical fragmentation of Fp(η¹-CH₂C₆H₅) and Me₂Si[C₅H₄Fe(CO)₂(η¹- CH₂C₆H₅)]₂ (2) to give metal-metal bonded species and bibenzyl as products has been explored. Several singly-bridged binuclear iron complexes have been prepared, namely Me₂Si[η⁵-C₅H₄Fe(CO)(L)I]₂(L = CO; L = PPh₃; L = P(OPh)₃) and [η⁵-C₅H₅Fe(CO)I]₂[(PhO)₂PC₂H₄P(OPh)₂], and their structure explored by both spectroscopic means and X-ray analysis. The preparation of the new metal-metal bonded complex, [η⁵-C₅H₅Fe(CO)]₂[(PhO)₂PC₂H₄P(OPh)₂], is also reported. Selective alkylations and reductions of the diiodide were L = PPh₃ with n-BuLi, benzylmagnesium chloride, and LiAlH₄ have led to the preparation of mixed alkyl-iodide and alkyl-hydride compounds. Molecular and crystal structures are determined for Me₂Si[η⁵-C₅H₄Fe(CO)]₂[dppm], Me₂Si[η⁵-C₅H₄Fe(CO)]₂[dppp], and Me₂Si[(η⁵- C₅H₄)₂Fe₂(CO)₃][dppm]. Full details on the synthesis, characterization, and the electrochemistry of the binuclear complexes Me₂Si[η⁵-C₅H₄Fe(CO)]₂[L] (where L = dppm, dppe, dppp) is reported. Also complexes of the type Me₂Si[(η⁵-C₅H₄)₂Fe₂(CO)₃][L] have been isolated in the case of L = dppm and dppe. A series of tetranuclear complexes for L = dppe and dppp is presented. A variety of activated unsaturated compounds, including acrylonitrile, react with Fp(η¹- C₅H₅), where Fp = η⁵- C₅H₅Fe(CO)₂, to give [3+2]-cycloadducts in good yield. Stereospecific replacement of the Fp moiety in these cycloadducts by a -CO₂Me group with retention of configuration occurs in good yield by oxidation with ammonium cerium (IV) nitrate in carbon monoxide saturated methanol. This two-step sequence: (3+2)-cycloaddition followed by oxidation, renders Fp(η¹- C₅H₅) a synthetic equivalent of methyl 1,3-cyclopentadiene-5-carboxylate in cycloaddition reactions. Sequential reaction of η⁵-C₅Me₅Fe(CO)₂I with AgBF₄, cyclopentadiene, and finally triethylamine affords the new compound η⁵- C₅Me₅Fe(CO)₂(η¹- C₅H₅) in 75% yield. This complex has been characterized by X-ray diffraction and low temperature NMR spectroscopy.

The scope of the cycloaddition reaction between .eta.-5-cyclopentadienyliron(II) dicarbonyl-.eta.-1-cyclopentadiene (1.12a) and electrophilic olefins (1.4) and acetylenes (1.5) producing 7-syn-.eta.-5-cyclopentadienyliron(II) dicarbonyl-.eta.-1-bicyclo 2.2.1 hept-5-enes (2.1) and 7-syn-.eta.-5-cyclopentadienyliron(II) dicarbonyl-.eta.-1-bicyclo 2.2.1 hept-2,5-dienes (2.2), respectively, is found to be general for non-sterically hindered olefins and bis-activated acetylenes. The range of reactive 1.4 compounds is extended to include some sterically hindered olefins through precoordination of the olefin to diethylchloroalane or ethyldichloroalane. In contrast to all other acyclic cis and trans-1,2-disubstituted olefins, maleonitrile (1.41) cycloadds with 1.12a with complete retention of alkene stereochemistry. The relative rates for the cycloaddition between 1.12a and 1.41 in benzene, dichloromethane, and methanol are found to be 1:2:4, respectively. These stereochemical and kinetic results are more consistent with a concerted 4+2 cycloaddition than a two-step dipolar 3+2 cycloaddition. A dramatic stereochemical dependence on solvent polarity is observed in the cycloadducts resulting from the reaction of 1.12a with 1.41. Depending on the solvent the Alder "endo" rule is obeyed (methanol) or flagrantly violated (benzene). Reaction of 2.1 with ammonium cerium(IV) nitrate, bromine, or chlorine in acetonitrile containing excess sodium azide gives bicyclo 2.2.1 hept-5-ene-7-syn-carbonylazides (3.4). The reaction is found to be general using 1,2-disubstituted 2.1 compounds with bromine or chlorine. The thermally induced rearrangement of 3.4 compounds in refluxing toluene-tert-butanol gives 7-syn-t-Boc-aminobicyclo 2.2.1 hept-5-enes (4.4) in good yield. This is the first high yield stereospecific synthesis of 4.4 compounds. Furthermore, the synthetic equivalency of 1.12a is shown to include 5-carbonylazide-1,3-cyclopentadiene (3.9) and 5-t-boc-amino-1,3-cyclopentadiene (4.5) as well as 5-carbomethoxy-1,3-cyclopentadiene (3.10) 11.12 .

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Thesis (M.Phil.)--Chinese University of Hong Kong. / Bibliography: leaves 78-80.

Thesis (M. Sc.)--York University, 2001. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references (leaves 77-83). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pMQ66415.

Thesis (Ph. D.)--Columbia University, 1942. / Vita. Bibliography: p. 19.

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