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Title: Synthetic inorganic chemistry : novel metallocenes and inorganic fullerenes
Author: Clancy, Gerald Patrick
ISNI:       0000 0001 3551 9126
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2000
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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}2PtI2 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 WO3-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)CHPMe2}2].
Supervisor: Green, M. L. H. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Cyclopentadiene ; Derivatives ; Synthesis ; Molybdenum oxides