This thesis concerns the new amine-substituted cyclopentadiene and indene ligands C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H which can co-ordinate to a metal through all five carbon atoms of the five-membered ring (η(^5)) and/ or through the nitrogen (σ). Chapter 1 reviews the recent literature concerning Lewis-base functionalised cyclopentadienyl and indenyl ligands and their compounds with s-, p-, d- and f-block metals. Chapter 2 contains a brief review of possible synthetic routes to amine-substituted cyclopentadienyl and indenyl ligands with some examples from the recent literature, and a detailed account of the synthesis of C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H. The amino alcohol (^t)BuNH(CH(_2))(_3) OH was synthesised by the conjugate addition of (^t)BuNH(_2) to ethyl acrylate and reduction of the product ester (^t)BuNH(CH(_2))(_2)C0(_2)Et using LiAIH(_4). (^t)BuNH(CH(_2))(_3)OH was converted into (^t)BuNH(CH(_2))(_3)Br.HBr and (^t)BuNH(CH(_2)(_3)Cl.HCl by reaction with HBr or SOCI(_2). Reaction between (^t)BuNH(CH(_2))(_3)C1.HC1 and two equivalents of Na(C(_5)H(_5)) gave C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H in good yield. Treatment of (^1)BuNH(CH(_2))(_3)C1.HC1 with excess NaOH followed by reaction with Li(C(_9)H(_7)) gave C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H, also in good yield. Chapter 3 describes the synthesis of various main group and iron compounds of C(_5)H(_5)(CH(_2))(_3)N((^t)Bu)H and C(_9)H(_7)(CH(_2))(_3)N((^t)Bu)H. Lithium salts Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H], Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)]Li, Li[C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)H] and Li[C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)]Li were prepared for use as reactive intermediates and Li[C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H] was characterised as its THF-adduct by (^t)H NMR spectroscopy. The silyl derivatives (Me(_3)Si)C(_5)H(_4)(CH(_2))(_3)NH(^t)Bu and (Me(_3)Si)C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)SiMe(_3) were synthesised and characterised by NMR spectroscopy, and (Me(_3)Si)C(_9)H(_6)(CH(_6))(_3)N((^t)Bu)H and (Me(_3)Si)C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)(SiMe(_3)) were also synthesised. The anune-substituted ferrocene Fe{η(^5)-C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H}(_2) was synthesised and oxidised to the corresponding ferricenium ion which was isolated as its PF(_6)(^-) salt. Exploratory work was carried out into the preparation of heterobimetallic species by reaction between Fe{η(^5)-C(_5)H(_4)(CH(_2))(_3)N((^t)Bu)H}(_2) and MX(_2) (M = Co, Ni, X = CI, M = Mn, X = Br). The substituted bis(indenyl) iron(II) complex Fe{η(^5)-C(_9)H(_6)(CH(_2))(_3)N((^t)Bu)H}(_2) was also synthesised. Chapter 4 is an account of the chemistry of {η(^5) :σ-C(_5)H(_4) (CH(_2))(_3)N(^t)Bu}Ti(NMe(-2))(_2) which was synthesised by an aminolysis reaction between C(_5)H(_5)(CH(_2))(_3)NH(^t)Bu and Ti(NMe(_2))(_4) Reaction between this compound and various weak acids gave a range of new compounds including{η(^5):σ-C(_5)H(_4)(CH(_2))(-3)N(^t)Bu} Ti(O(^t)Pr)(_2), {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu)(_2), {η(^5):σC, {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(C(_5)H(_5))(NMe(_2)) , {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(SnBu(_3))(_z) and the imido-bridged dimer [{η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(NHPh)](_2)(µ-NPh)2, the X-ray structure of which is reported. Chapter 5 describes the experimental procedures used, and chapter 6 gives lists of characterising data for each compound. Appendix A gives details of the methods used for magnetic susceptibility determinations; appendix B lists X-ray crystallographic data for [ {η(^5):σ-C(_5)H(_4)(CH(_2))(_3)N(^t)Bu}Ti(NHPh)](_2)(µ-NPh)(_2) and appendix C lists departmental colloquia attended.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:337977 |
| Date | January 1997 |
| Creators | Marsh, Sarah Margaret Beatrice |
| Publisher | Durham University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://etheses.dur.ac.uk/5012/ |
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