Synthesis, characterization, and reactivity of iron complexes with N-donor ligands in relation to oxygenation of hydrocarbons
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- Tez No: 400756
- Danışmanlar: PROF. PERICLES STAVROPOULOS
- Tez Türü: Doktora
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 2004
- Dil: İngilizce
- Üniversite: Boston Unıversıty
- Enstitü: Yurtdışı Enstitü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
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Özet (Çeviri)
This study examines structural and functional aspects of reactivity of Gif-type reagents, which depend on dioxygen and zinc in pyridine/pivalic acid mixtures. In these solutions, the -oxo bridged [Fe3O(O2CCMe3)6(py)3] is reduced by Zn to generate [Fe(II)(O2CCMe3)2(py)4], which readily reverts to [Fe3O(O2CCMe3)6(py)3], and eventually to [Fe3O(O2CCMe3)6(py)3]+, upon exposure to dioxygen. All three species mediate Gif-like oxygenation of substrates supported by O2/Zn and to a smaller extent by H2O2. Product profiles are indicative of competition between dioxygen and protonated pyridine to capture tert- and sec-alkyl radicals. The tert/sec selectivities and other diagnostic parameters are consistent with those of other Gif-type oxygenations, suggesting ix the involvement of HO? and a more selective, substrate-based tert-alkoxyl radical. All-ferric [Fe(III)3O(O2C-CMe3)6(L)3]+ (L=H2O, py) are converted by H2O2 to the hexairon(III) peroxo compounds [Fe6(O2)(O)2(O2CCMe3)12(L)2] (L = Me3CCO2H, py), (between 7-80 % yield) which feature a [Fe6(?2-?4-O2)(?3-O)2] core, and are not involved in Gif oxygenations. The second part of this dissertation explores the synthesis and reactivity of a series of metal complexes containing novel ligands (L1H3):[(4-tert-Butyl-C6H4)-NH-(ortho-C6H4)]3N and (L2H3):[(3,5-di-tert-Butyl-C6H3)-NH-(ortho-C6H4)]3N. The ferrous species [(L1)Fe(II)-NCMe][Ph4P] is a crystallographically characterized representative of a series of complexes of type [(L1)Fe(II)-solv]? (solv = NCCH3, DMF, THF). These complexes are exceedingly air sensitive and can be readily oxidized by dioxygen to afford [(L)Fe(III)-solv], [(L)Fe(III)-OH]? (K+ or PPh4+ salts) and [(L1re-1)Fe(III)-O-Fe(III)(L1re-1)] depending on the solvent used. The most intriguing product is [(L1re-1)Fe(III)-O-Fe(III)(L1re-1)], which features ligand rearrangement amounting to a formal 1,4-phenyl migration. This is also accompanied by one-electron oxidation of the ligand, localized onto an aromatic amine/imine moiety. The ligand is also capable of sustaining a two-electron oxidation, as observed in the reaction of [(L)Fe(III)-solv] with FeCl3, to afford [(L1re-2H)(Cl)Fe(II)-(?-Cl)2-Fe(II)(Cl)(L1re-2H)]. Ligand rearrangement is also observed with other redox active metals. For instance, [(L)Mn(II)-THF]? is oxidized by dioxygen to [(L1re-1)Mn(III)-(?-O)2-Mn(III)(L1re-1)]. Changing metal center to CrCl3 afforded [(L)Cr(III)-THF] and [(L1re-1)(Cl)Cr(III)-THF]. Regardless of the metal center employed, reactions of ligand (L2H3) afforded the mononuclear complexes [(L2re)M(III)-THF], where M = Fe, Cr, and V. The ligand is rearranged as usual, but is not oxidized. Mechanisms accounting for oxidative ligand rearrangement are also presented.
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