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Durham e-Theses
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Studies in early transition metal organometallic chemistry

Kingsley, Andrew James (1998) Studies in early transition metal organometallic chemistry. Doctoral thesis, Durham University.



The work in this thesis is separated into two sections: Chapters 1 to 6 are concerned with the synthesis and characterisation of amide functionalised cyclopentadienyl complexes of Group 4, 5, 6 and 8 transition metals. Chapters 7 to 9 involve a study into complexes containing potential a-agostic interactions. Chapter 1 provides an introduction to functionalised cyclopentadienyl complexes and also to the ligand C(_5)H(_5)(CH(_2))(_3)N(H)Me. Chapter 2 describes the synthesis of the Group 6 complexes of tungsten and molybdenum, M[ƞ(^5):ƞ(^1)-C(_5)H(_4)(CH(_2))(_3)NMe](NR)(_2) by different routes, their chemistry, and subsequent reactions. Chapter 3 covers the preparation of the Group 4 complexes of zirconium and titanium, M[ƞ(^5):ƞ -C(_5))H(_4)(CH(_2))(_3)NMe](C(_5)H(_5))Cl, their subsequent reactions, and potential as olefin polymerisation catalysts. Chapter 4 contains the synthesis of the Group 5 complexes of niobium and tantalum, M[ƞ(^5):ƞ(^1)-C(_5)H(_4)(CH(_2))(_3)NMe](N(^t)Bu)(NH(^t)Bu).Chapter 5 deals with the preparation of the Group 5 and 6 vanadium and chromium chloride complexes M[ƞ(^5):ƞ(^1)-C(_5)H(_4)(CH(_2))(_3)NMe]Cl, their reactions, and potential as olefin polymerisation catalysts. Chapter 6 descibes the preparation of some iron complexes. The synthesis of the ferrocene, Fe[ƞ(^5)-C(_5)H(_4)(CH(_2))(_3)N(H)Me](_2), and the bridged carbonyl complex, {Fe[ƞ(^5):ƞ(^1)-C(_5)H(_4)(CH(_2))(_3)N(H)Me](CO)(μ-CO)}(_2), are described. Chapter 7 provides an introduction to a-agostic interactions, the use of the Isotopic Perturbation of Resonance (IPR) technique as a means of characterisation, and the preparation of deuterated starting materials to perform such investigations. Chapter 8 investigates the complexes MeTiC(_3)L (L = dme, tmeda, diphos), W(N(^t)Bu)(_2)Me(_2), and Mo(N-(_2),(_6)-(^i)Pr(_2)C(_6)H(_3))(_2)Me(_2) for a-agostic interactions, using the IPR technique Chapter 9 describes the synthesis of and investigation for a-agostic bonds in zirconium and titanium neopentyl chloro complexes MNp(_x)Cl(_4-x) (x = 1 - 4).The Appendices outline the preparative and analytical methods used, and X-ray crystallographic data.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1998
Copyright:Copyright of this thesis is held by the author
Deposited On:13 Sep 2012 15:56

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