The synthesis of phosphonium indenylides and an investigation of their coordination to group 4 metals by Shalyn

ii
 Acknowledgements iii
 Table of Contents iv
 List of Tables vi
 List of Figures vii
 List of Abbreviations ix
 Chapter 1. Introduction 1
 1.1 The Ramirez Ylide 1
 1.1.1 Synthesis of Phosphonium Cyclopentadienylides 2
 1.1.1.1 Synthesis of the Ramirez Ylide 3
 1.1.1.2 Synthesis via Diazocyclopentadienes 3
 1.1.1.3 Synthesis via Chlorodiphenylphosphine 5
 1.1.2 Coordination of the Ramirez Ylide and Derivatives 7
 1.1.2.1 Group 4 Complexes 7
 1.1.2.2 Group 6 Complexes 11
 1.2 Indenyl-derived ylides 14
 1.2.1 Croft’s Synthesis of the Indenylide 15
 1.2.2 Rufanov Synthesis of the Indenylide 16
 1.2.3 Brownie Synthesis of the Indenylide 17
 1.2.4 Coordination Complexes of Indenylides 18
 1.2.4.1 Coordination to Group VI metals 20
 1.3 Aims of Present Research 21
 Chapter 2. Experimental 23
 2.1 General Conditions 23
 2.2 X-ray Crystal Structure Determinations 24
 2.3 Preparation of the Ligands of the Type C9H6PR3 25
 2.3.1 Synthesis of 1-Bromoindene 25
 2.3.1.1 Synthesis of Indenyl Lithium 25
 2.3.1.2 Synthesis of Trimethylsilyl(indene) 25
 2.3.1.3 Synthesis of Dioxane Dibromide 26
 2.3.1.4 Synthesis of 1-(bromoindene) 26
 2.3.2 Synthesis of Phosphonium Salts of the Type [C9H7PR3]X 27
 2.3.2.1 Synthesis of [C9H7PPh3]Br (Ιa) 27
 2.3.2.2 Synthesis of [C9H7PMePh2]Br (Ιb) 28
 2.3.2.3 Synthesis of [C9H7PMe2Ph]Br (Ιc) 29
 2.3.2.4 Synthesis of [C9H7PMePh2]PF6 (Ιd) 29
 2.3.3 Synthesis of Indenyl Ylides, C9H6PR3 30
 2.3.3.1 Synthesis of C9H6PPh3 (ΙΙa) 30
 2.3.3.2 Synthesis of C9H6PMePh2 (ΙΙb) 30