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Studies in Early Transition Metal Organometallic Chemistry Durham E-Theses Studies in early transition metal organometallic chemistry Kingsley, Andrew James How to cite: Kingsley, Andrew James (1998) Studies in early transition metal organometallic chemistry, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/4846/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk studies in Early Transition Metal Organometallic Chemistry A thesis submitted in part fulfilment of the degree of Doctor of Philosophy Andrew James Kingsley Grey College, University of Durham February 1998 The copyright of this thesis rests with the author. No quotation from it should be published without the written consent of the author and information derived from it should be acknowledged. 2 Alio M Statement of Copyright The copyright of this thesis rests with the author. No quotation from it should be published without his prior consent and information derived from it should be acknowledged. Declaration The work described in this thesis was carried out at the University of Durham, Department of Chemistry, between October 1994 and September 1997. All the work is my own unless stated otherwise, and it has not been submitted previously for a degree at this or any other university. Publications 1) Titanium and Zirconium Neopentyl Chloro Complexes, MNpxCU-x (x = 1-4); A.K. Hughes and A.J. Kingsley, J. Organomet. Chem., 1997, 539, 109. 2) Novel Synthesis of Linked Cyclopentadienyl-Amide Complexes; A.K. Hughes and A.J. Kingsley, J. Chem. Soc, Dalton Trans., 1997, 4139. 3) Unexpected Co-Crystallisation of Monomeric and Dimeric Molybdenum Bis Imido Complexes; A. Bastanov, J.A.K. Howard, A.K. Hughes, A.J. Kingsley, J.M. Rawson and D.F. Wass, Polyhedron, submitted 1997. Acknowledgements First and foremost, I would like to thank my supervisor Dr. Andrew Hughes for his continued support and encouragement throughout the last three years, without which this thesis would not have been possible. I'd like to thank all the occupants of lab 108, who have made the last three years that much more enjoyable; Brian Bridgewater, Patrick Gemmell, Andrew Johnson, Sarah Marsh, Mark Roden and Melanie Thompson. All the inorganic groups deserve a special thankyou for making it such a hip and happening section. On the technical side, thanks must also go to Gordon Haswell and Ray Hart for their glassblowing, Julia Say and Alan Kenwright for their NMR services, Mike Jones and Lara Turner for mass spectroscopic analysis, Jaraka Dostal for elemental analysis, Brian Hall for standardising many a bottle of "BuLi, and Judith Howard, Angus Mackinnon, Christian Lehmann, Janet Moloney and Roy Copley for X-ray crystallography. 1 would like to give special thanks to Andrew Johnson for his enthusiasm and gathering of odds and ends for this thesis. Finally, I thank my Mum, Dad and Michael for continuous support throughout. ni Abstract The work in this thesis is separated into two sections: Chapters 1 to 6 are concerned with the synthesis and characterisation of amide fimctionalised 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 infroduction to functionalised cyclopentadienyl complexes and also to the ligand C5H5(CH2)3N(H)Me. Chapter 2 describes the synthesis of the Group 6 complexes of tungsten and molybdenum, M[Ti^:ri'-C5H4(CH2)3NMe](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[ri*:r|'-C5H4(CH2)3NMe](C5H5)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[ri*:Ti'-C5H4(CH2)3NMe](N'Bu)(NH'Bu). Chapter 5 deals with the preparation of the Group 5 and 6 vanadium and chromium chloride complexes M[r|^:ri'-C5H4(CH2)3NMe]Cl, their reactions, and potential as olefin polymerisation catalysts. Chapter 6 descibes the preparation of some iron complexes. The synthesis of the ferrocene, Fe[r|^-C5H4(CH2)3N(H)Me]2, and the bridged carbonyl complex, {Fe[r|^:ri'- C5H4(CH2)3N(H)Me](CO)(^-CO)}2, are described. Chapter 7 provides an infroduction 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^L (L = dme, tmeda, diphos), W(N'Bu)2Me2, and Mo(N-2,6-'Pr2C6H3)2Me2 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 MNpxCU-x (x = 1 - 4). The Appendices outline the preparative and analytical methods used, and X-ray crystallographic data. iv Abbreviations "Bu "Butyl group, C4H9 'Bu ^Butyl group, C(CH3)3 *Pr Isopropyl group, CH(CH3)2 Ph Phenyl group, CeHs Me Methyl group, CH3 Np Neopentyl group, CH2C(CH3)3 Ts Tosylate group, 3-CH3C6H4SO2 Ar" 2,6-[(CH3)2CH]2C6H3 Ar^ 3-CF3C6H4 dmpe Dimethylphosphinoethane, CH3PCH2CH2PCH3 dme 1,2-dimethoxyethane, CH3OCH2CH2OCH3 tmeda N,N,N',N'-tetramethylethylenediamine, (CH3)2NCH2CH2N(CH3)2 diphos 1,2-bis(diphenylphosphino)ethane, Ph2PCH2CH2PPh2 THF Tetrahydrofiiran, C4H8O TMS Trimethylsilyl, (CH3)3Si DMSO Dimethyl Sulphoxide, (CH3)2SO HMPA Hexamethylphosphoramide L General two electron ligand X General one electron ligand Z Carbon or silicon bridge R Any hydrocarbon group CpH Cyclopentadiene, CeHs CpNMe C5H4(CH2)3NMe FAL Tris Fluoro Alkyl Aluminoxane MAO Methyl Aluminoxane, [AlOMeJn IR Infra-Red NMR Nuclear Magnetic Resonance COSY correlation Spectroscopy HETCOR HETeronuclear CORrelation NOE Nuclear Overhauser Effect MO Molecular Orbital HOMO Highest Occupied Molecular Orbital IPR Isotopic Perturbation of Resonance Abbreviations for IR and NMR spectra s singlet d doublet t triplet q quartet quin quintet sept septet m multiplet br broad A5 A[6(CH3) - 5(CH2D)] S solvent * impurity VI Contents Chapter 1 - Introduction to Amide Functionalised Cyclopentadienyl Complexes 1.1 Metal-Cyclopentadienyl Chemistry 1 1.1.1 Metallocenes 1 1.1.2 Bis cyclopentadienyl complexes (araa-metallocenes) 2 1.1.3 Functionalised cyclopentadienyl complexes 3 1.2 LX Functionalised Cyclopentadienyl Systems 6 1.2.1 Complexes with amide functionalised cyclopentadienyl ligands 6 1.2.2 Alkyl and hydrido complexes 10 1.2.3 Structure 12 1.2.4 Complexes with alkoxo fimctionalised cyclopentadienyl ligands 14 1.2.5 Complexes with polydentate amide functionalised 16 cyclopentadienyl ligands 1.3 Application of Amide Functionalised Cyclopentadienyl 17 Complexes in Catalysis 1.3.1 Ziegler-Natta catalysis 17 1.3.2 Polymerisation of ethylene and a-olefms 17 1.3.3 Hydrogenation and hydroboration 20 1.4 Preparation of Amide Functionalised Cyclopentadienyl Complexes 22 1.4.1 Synthesis of amine functionalised cyclopentadienyl ligands 23 1.4.2 Synthesis of C5H5(CH2)3N(H)Me, 1.1 23 1.4.3 Synthesis of lithium salts: a) [C5H4(CH2)3N(H)Me]Li. 1.2 27 b) [C5H4(CH2)3NMe]Li2,1.3 29 1.4.4 Synthesis of [C5H4(CH2)3NMe](SiMe3)2,1.4 29 1.4.5 Previous work with C5H5(CH2)3N(H)Me, 1.1 30 1.5 Aims 33 1.6 Experimental 34 1.6.1 Preparation of C5H5(CH2)3N(H)Me, 1.1 34 1.6.2 Preparation of [C5H4(CH2)3N(H)Me]Li, 1.2 37 1.6.3 Preparation of [C5H4(CH2)3NMe]Li2,1.3 37 1.6.4 Preparation of [C5H4(CH2)3NMe](SiMe3)2,1.4 37 1.7 References 38 vii Chapter 2 - Group 6 - Tungsten and Molybdenum Amide Functionalised Cyclopentadienyl Complexes. 2.1 Infroduction 42 2.1.1 Bis-cyclopentadienyl (a«5a) complexes 42 2.1.2 Nifrogen fiinctionalised cyclopentadienyl complexes 43 2.1.3 Aims 45 2.2 Synthesis of Amide Functionalised Cyclopentadienyl Complexes 46 2.2.1 Reaction between W(N*Bu)2(NrfBu)2 and C5H5(CH2)3N(H)Me, 1.1 46 2.2.2 Reaction between Mo(N'Bu)2Cl2dme and [C5H4(CH2)3NMe]Li2,1.3 49 2.2.3 Reaction between Mo(NAr)2Cl2dme and [C5H4(CH2)3NMe]Li2,1.3 52 2.2.4 Molecular and elecfronic structures of 2.2 - 2.5 54 2.3 Reactions of Mo[ti^:-n'-C5H4(CH2)3NMe](N'Bu)2,2.3 59 2.3.1 Reaction between ethyl bromide and 2.3 60 2.3.2 Attempted reaction between dimethyl ammonium chloride and 2.3 62 2.3.3 Attempted reaction between aniline and 2.3 62 2.3.4 Attempted reaction between benzophenone and 2.3 63 2.4 Sunmiary . 63 2.5 Experimental 64 2.5.1 Preparation of starting materials 64 2.5.2 Preparation ofW[Ti^:Ti'-C5H4(CH2)3NMe](N'Bu)2, 2.2, including 65 the intermediate W[Ti'-C5H5(CH2)3NMe](NH'Bu)2(N'Bu)2, 2.1 2.5.3 Preparation of Mo[Ti^:ri^-C5H4(CH2)3NMe](N'Bu)2, 2.3 67 2.5.4 Preparation of Mo[Ti^:Ti'-C5H4(CH2)3NMe](NAr^)2, 2.4 68 2.5.5 Preparation of Mo[Ti^:-n'-C5H4(CH2)3NMe](NAr")2,2.5 69 2.5.6 Preparation of Mo[Ti^Ti'-C5H4(CH2)3N(Et)Me]Br(N'Bu)2, 2.6 70 2.5.7 Attempted reaction between dimethyl ammonium chloride and 2.3 71 2.5.8 Attempted reaction between aniline and 2.3 71 2.5.9 Attempted reaction between benzophenone and 2.3 71 2.6 References 72 Vlll Chapter 3 - Group 4 - Zirconium and Titanium Amide Functionalised Cyclopentadienyl Complexes.
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