Tesis: "Inorganic chemistry"

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Clancy, Gerald Patrick. "Synthetic inorganic chemistry : novel metallocenes and inorganic fullerenes". Thesis, University of Oxford, 2000. http://ora.ox.ac.uk/objects/uuid:9c7f7c35-bb8f-4117-8e2e-e56a9fbcbeab.

Texto completo

Resumen

This thesis is divided into two parts. The first part concerns the synthesis and characterisation of substituted metallocene complexes of the transition and main group metals. The second part describes the preparation and characterisation of inorganic fullerene (IF)-related materials. Chapter 1 reviews the chemistry of dialkyl- and diaryl-phosphino substituted cyclopentadienyl complexes of the transition metals. Chapter 2 describes the synthesis and characterisation of the new ligands [M(C₅Me₄)CH₂PMe₂] (M = H, Li, Na and K) via the precursors [HC₅Me₄)CH₂PHMe₂][X] (X = Cl and PF₆). The synthesis, characterisation and chemical reactivity of the compounds [Zr{{η-C₅Me₄)CH₂PMe₂}₂Cl₂ and [Mn{η-C₅Me₄)CH₂PMe₂}₂] is reported together with supporting evidence for the synthesis of the bimetallic complex [Zr{U+03B7-C₅Me₄)CH₂PMe₂}₂Cl₂PtI₂] and the complex [Mn{η-C₅Me₄)CH₂PMe₂B(C₆F₅)₃}₂]. Chapter 3 provides a brief introduction into the field of main group metallocenes and describes the synthesis and characterisation of the new main group metallocenes [M{η- C₅H₄)CMe₂PMe₂}₂] (M = Pb and Sn). The B(C₆F₅)_{3 adduct [Pb{η-C₅H₄)CMe₂PMe₂(B(C₆F₅)₃}₂] has also been synthesised. The main group - transition metal bimetallic complex [Pb{η-C₅H₄)CMe₂PMe₂}₂PtI_{2_{in which the substitutedplumbocene acts as a bidentate ligand, has been characterised by mass spectrometry and ³¹P{¹H}NMR spectroscopy. Chapter 4 provides an introduction into the field of IF-related materials and an overview of the analytical techniques used in their characterisation. Chapter 5 describes the preparation and characterisation of IF-MoS₂ and IF-(Nb,W)S₂ materials from MoC and the binary oxides Nb₈ W₉O₄₇ and Nb₄W₁₃O₄₇ respectively. A powder X-ray diffraction study of the conversion of WC to WO_3-X and the subsequent sulfidisation by H₂S to form novel IF-WS₂ morphologies is also described. Chapter 6 describes the preparation of amorphous Group 5 metal (V, Nb and Ta) oxides using the metal vapour synthesis technique. These amorphous precursors have been annealed in a reducing atmosphere to form the oxide phases U+03B1-V₂O₃, NbO₂ and TT-Ta₂O₅ which have been identified by powder X-ray diffraction. Upon reaction with H₂S, the crystalline oxides afford layered sulfides of the form MS₂ (M = V, Nb and Ta), some of which exhibit behaviour typical of IF-like materials and have been characterised by HRTEM, powder X-ray diffraction and EDX analysis. Chapter 7 outlines the experimental details for the synthesis, characterisation, reactions and compounds described in the preceding chapters. Chapter 8 presents the characterising data for the new compounds described in chapters 2 and 3. Appendix A contains details of the crystallographic data for the structurally characterised compound [Mn{η-C₅Me₄)CH_PMe₂}₂].}}}