The synthesis and reactivity of functionalised alkyl transition metal complexes

 

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dc.contributor.advisor Moss, John R en_ZA
dc.contributor.author Friedrich, Holger Bernhard en_ZA
dc.date.accessioned 2016-10-24T03:50:38Z
dc.date.available 2016-10-24T03:50:38Z
dc.date.issued 1990 en_ZA
dc.identifier.citation Friedrich, H. 1990. The synthesis and reactivity of functionalised alkyl transition metal complexes. University of Cape Town. en_ZA
dc.identifier.uri http://hdl.handle.net/11427/22277
dc.description Includes bibliographical references. en_ZA
dc.description.abstract The complexes [CpFe(CO)₂CH₂X] and [CpW(CO)₃CH₂X] (Cp = n⁵-C₅H₅; X=Cl, Br, I) have been prepared and their reactivity with a series of tertiary phosphines, amines, SMe₂ and AsPh₃ in THF, CH₃CN and MeOH has been investigated. Two types of cationic products, namely the ylide complexes [CpM(CO)nCH₂L]+ or the disubstituted complexes [CpML₂(CO)n-l]+ (M = Fe, n = 2; M = W, n = 3) were obtained, depending on the halide (X), the ligand (L), the metal (M) and the solvent used. The variables X, L, M and the solvent used were also all found to influence the rates of the reactions. Thus the relative reaction rates of the complexes [CpFe(CO)₂CH₂Br] and [CpW(CO)₃CH₂Br] with L were determined by 1 H NMR spectroscopy and found to increase with increasing pKa and decreasing cone angle of L. In general, the rate of reaction of [CpFe(CO)₂CH₂X] and [CpW(CO)₃CH₂X] with L increases in the sequence Cl < Br < l and the reactions of [CpFe(CO)₂CH₂X] with L are significantly faster than the corresponding reactions of [CpW(CO)₃CH₂X]. The reactions of [CpFe(CO)₂CH₂Br] and [CpW(CO)₃CH₂Br] with dppe {dppe = bis(diphenylphosphino)ethane} yield the bridged dicationic ylide complexes [{Cp(CO)₂FeCH₂}₂{PPh₂(CH₂)₂PPh₂}] and [{Cp(CO)₃WCH₂}₂{PPh₂(CH₂)₂PPh₂}] respectively. en_ZA
dc.language.iso eng en_ZA
dc.subject.other Chemistry en_ZA
dc.subject.other Inorganic Chemistry en_ZA
dc.title The synthesis and reactivity of functionalised alkyl transition metal complexes en_ZA
dc.type Doctoral Thesis
uct.type.publication Research en_ZA
uct.type.resource Thesis en_ZA
dc.publisher.institution University of Cape Town
dc.publisher.faculty Faculty of Science en_ZA
dc.publisher.department Department of Chemistry en_ZA
dc.type.qualificationlevel Doctoral
dc.type.qualificationname PhD en_ZA
uct.type.filetype Text
uct.type.filetype Image
dc.identifier.apacitation Friedrich, H. B. (1990). <i>The synthesis and reactivity of functionalised alkyl transition metal complexes</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/22277 en_ZA
dc.identifier.chicagocitation Friedrich, Holger Bernhard. <i>"The synthesis and reactivity of functionalised alkyl transition metal complexes."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 1990. http://hdl.handle.net/11427/22277 en_ZA
dc.identifier.vancouvercitation Friedrich HB. The synthesis and reactivity of functionalised alkyl transition metal complexes. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 1990 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/22277 en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Friedrich, Holger Bernhard AB - The complexes [CpFe(CO)₂CH₂X] and [CpW(CO)₃CH₂X] (Cp = n⁵-C₅H₅; X=Cl, Br, I) have been prepared and their reactivity with a series of tertiary phosphines, amines, SMe₂ and AsPh₃ in THF, CH₃CN and MeOH has been investigated. Two types of cationic products, namely the ylide complexes [CpM(CO)nCH₂L]+ or the disubstituted complexes [CpML₂(CO)n-l]+ (M = Fe, n = 2; M = W, n = 3) were obtained, depending on the halide (X), the ligand (L), the metal (M) and the solvent used. The variables X, L, M and the solvent used were also all found to influence the rates of the reactions. Thus the relative reaction rates of the complexes [CpFe(CO)₂CH₂Br] and [CpW(CO)₃CH₂Br] with L were determined by 1 H NMR spectroscopy and found to increase with increasing pKa and decreasing cone angle of L. In general, the rate of reaction of [CpFe(CO)₂CH₂X] and [CpW(CO)₃CH₂X] with L increases in the sequence Cl < Br < l and the reactions of [CpFe(CO)₂CH₂X] with L are significantly faster than the corresponding reactions of [CpW(CO)₃CH₂X]. The reactions of [CpFe(CO)₂CH₂Br] and [CpW(CO)₃CH₂Br] with dppe {dppe = bis(diphenylphosphino)ethane} yield the bridged dicationic ylide complexes [{Cp(CO)₂FeCH₂}₂{PPh₂(CH₂)₂PPh₂}] and [{Cp(CO)₃WCH₂}₂{PPh₂(CH₂)₂PPh₂}] respectively. DA - 1990 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1990 T1 - The synthesis and reactivity of functionalised alkyl transition metal complexes TI - The synthesis and reactivity of functionalised alkyl transition metal complexes UR - http://hdl.handle.net/11427/22277 ER - en_ZA


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