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Title: Organometallic chemistry of molybdenum and cobalt and related studies
Author: Aviles, Teresa
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 1978
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The thesis concerns developments in the chemistry of mono- cyclopentadienylmolybdenum derivatives and (η-allylic)monocyclopentadienylcobalt derivatives. Improved synthetic routes to the compound (Mo{η-C5H5}2dppe)(PF6)2 are described. It is shown that there are structural isomers of the compound Mo{η-C5H5}{η-C5H6}dppe)PF6 which differ in the orientation of the η-C5H6 ligand on the metal. The new compounds (Mo{η-C5H5}2dppm)(PF6)2, (Mo{η-C5H5}2{dppm}H)PF6, (Mo{η-C5H5}2{dppm}Cl)PF6, and (Mo{η-C5H5}2{NC-CH3}2) have been prepared. The new compound Mo{η-C5H5}{dppe}H3 has been synthesised by treatment of Mo{η-C5H5}{dppe}Cl3 with NaAlH2(OCH2CH2OCH3)2. The reaction of the trihydride with butadiene led to isomers of the compound Mo{η-C5H5}{1-CH33-C3H4}dppe. These undergo hydride abstraction giving isomers of the compound (Mo{η-C5H5}{η4-C4H6}dppe)PF6. New synthetic routes to the compound Mo{η-C5H5}{dppe}H3 were investigated. Treatment of Mo{η-C5H5}{dppe}Cl3 with NaBH4 and separately with HSn{n-butyl}3 gave the new compounds Mo{η-C5H5}{dppe}BH4 and Mo{η-C5H5}{dppe}{Sn(n-butyl)3}H2 respectively. The new compounds Mo{η-C5H5}{η3-C5H7}dppm and Mo{η-C5H5}{dppm}Cl3 have also been prepared and characterised. The chemistry of the (η-allylic)monocyclopentadienylcobalt system was studied with a view to understanding the factors leading to regiospecific addition on the polyene ligands of organometallic cations. The new compounds (Co{η-C5H5}{η-C3H5}PR3)(PF6), (PR3 = PPhMe2, PMe3), (Co{η-C5H5}{1-CH3-η-C3H4}L)(PF6) (L = CO, PMe3), (Co{η-C5H5}{2-CH3-η-C3H4}L) (PF6) , (L = CO, PMe3, Py, NH3) , Co{η-C5H5}{2-CH3-η-C3H4}I and Co{η-C5H5}(1-CH3-η-C3H4}Br were prepared and characterised. The reactions of many of these compounds towards addition of hydride or methyl anion were studied. New reactions observed included the reaction of (Co{η-C5H5}{η-C3H5}PMe3)PF6 with MeLi to give the unexpected product Co{η-C5H5}{PMe3}Me2. Reaction of Co{η-C5H5}(CO}I2 with PMe3 gave (Co{η-C5H5}{PMe3}3)I2. Treatment of (Co{η-C5H5}{PMe3}3)(PF6)2 with MeLi gave Co{η-C5H5}{PMe3}Me2. The compound (Co{η-C5H5}{PPhMe2}2H)PF6 was isolated in the reaction of Co{η-C5H5}{PPhMe2}I2 with isopropyl magnesium bromide. The Introductory Chapter of the thesis reviews known chemistry pertinent to the studies described above.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available