Durham E-Theses A study of transition metal compounds in liquid hydrogen chloride Symon, David Allen How to cite: Symon, David Allen (1972) A study of transition metal compounds in liquid hydrogen chloride, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/9115/ 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 To Tina INDEX PREFACE i ACKNOWLEDGEMENTS ii SUMMARY iii CHAPTER I INTRODUCTION 1 1.1.1 Non-Aqueous Solvents 1 1.1.2 History 2 1.1.3 Theory of the Solvent 9 1.2 Protonation of neutral transition metal complexes 14 1.2.1 History 14 CHAPTER 2 EXPERIMENTAL TECHNIQUES 18 2.1 The Vacuum System 18 2.2 Apparatus 23 2.3 Inert Atmosphere Glove Box Techniques 29 2.4 Determination of physical properties 30 2.4.1 Infrared spectra 30 2.4.2 '''H Nuclear Magnetic resonance studies 42 2.4.3 Ultra violet/visible spectra 45 2.4.4 "^Fe Mossbauer studies 45 2.4.5 Electron spectroscopy studies 45 2.5 Analytical techniques 46 2.5.1 Estimation of carbon, hydrogen and nitrogen 46 2.5.2 Estimation of chlorine, bromine and iodine 46 2.5.3 Estimation of iron 47 2.5.4 Estimation of phosphorus 47 2.6 Preparation and purification of reagents 47 2.6.1 Hydrogen chloride 47 2.6.2 Boron trichloride 49 CHAPTER 2 2.6.3 Phosphorus pentafluoride 49 2.6.4 Chlorine 50 2.6.5 Nitrosyl chloride 51 2.6.6 Deuterium Chloride 51 2.6.7 Sulphur dioxide 51 2.6.8 Bis(w-cyclopentadienyldicarbonyl iron (I)) 52 2.6.9 rc-cyclopentadienyldicarbonyl iron(II) chloride 53 2.6.10 it-cyclopentadienyldicarbonyl iron(ll) bromide 53 2.6.11 it-cyclopentadienyldicarbonyl iron(ll) iodide 53 2.6.12 n-cyclopentadienyltricarbonyl iron(II) chloride 54 2.6.13 Tt-cyclopentadienyldicarbonyl iron a-methyl 54 2.6.14 Tetrakis(TC-cyclopentadienylcarbonyl iron(l)) 55 2.6.15 Tetracarbonyl iron dibromide 57 2.6.16 Tetracarbonyl iron di-iodide 61 CHAPTER 3 REACTIONS OF BIS(TC-CYCLOPENTADIENYLDICARBONYL IRON(l)) IN LIQUID HYDROGEN CHLORIDE 62 3.1 Introduction 62 3.2 Results and Discussion 62 3.3 Experimental 77 CHAPTER 4 REACTIONS OF TC-CYCLOPENTADIENYLDICARBONYL IRON (II) HALIDES (CHLORIDE, BROMIDE AND IODIDE) AND OF TC-CYCLOPENTADIENYLTRICARBONYL IRON (II) CHLORIDE IN LIQUID HYDROGEN CHLORIDE 85 4.1 Results and Discussion 85 4.2 Experimental 90 CHAPTER 5 REACTIONS OF TETRAKIS(TI-CYCLOPENTADIENYLCARBONYL IRON(I)) 99 5.1 Results and Discussion 99 5.2 Experimental 114 CHAPTER 6 STUDIES ON THE TI-CYCLOPENTADIENYLDICARBONYL IRON -u-HALOGEN Tt-CYCLOPENTADIENYLDICARBONYL IRON CATIONS, 120 + [(it-C5H5)Fe(CO)2]2X , X = CI, Br, or I. 6.1 Results and Discussion 120 6.2 Experimental Section 138 CHAPTER 7 ELECTRON SPECTROSCOPY AND 57Fe MOSSBAUER SPECTROSCOPY 140 7.1 Electron spectroscopy 140 7.1.1 Introduction 140 7.1.2 Results and discussion 151 7.2 "*^Fe Mossbauer Spectroscopy 168 7.2.1 Introduction 168 7.2.2 Results and discussion 171 CHAPTER 8 FAR INFRARED SPECTRAL STUDIES 186 8.1 Introduction 186 8.1.1 Advantages of interferometry over conventional spectroscopic techniques 187 8.1.2 Theory 191 8.1.3 Instrumentation 196 8.1.4 Computation 197 8.2 Results and discussion 201 8.2.1 Examination of water vapour spectrum 201 8.2.2 Metal carbonyl halides 212 8.2.3 Ti-cyclopentadienylcarbonyl iron complexes 223 CHAPTER 9 CONCLUSIONS AND FUTURE WORK 231 9.1 Acid-base reactions 231 9.2 Oxidation reactions 232 9.3 Structure of the u-cyclopentadienyldicarbonyl iron-u-halogeno n-cyclopentadienyldicarbonyl iron cations. 232 9.4 Techniques available 9.4.1 Infrared spectroscopy 233 9.4.2 "^Fe Mossbauer Spectroscopy 234 9.4.3 uv/visible spectroscopy 234 APPENDIX A. Computer program for storing data from paper tapes obtained from FS-720 236 Fourirer transform program 239 Graph Plotter program 269 APPENDIX B. ESTIMATION OF PHOSPHORUS 277 APPENDIX C. MAGNETO CHEMISTRY OF THE TETRAKIS(rc-CYCLOPENTADIENYL CARBONYL IRON) CATION 280 REFERENCES 283 PRELIMINARY X-RAY CRYSTAL STRUCTURE DATA 290 INDEX OF ILLU STRATION S Figure 2.1 The Vacuum System 19 Plate 2.1 The Vacuum System 20 Figure 2.2 Rotaflo TF6/13 ampoules 24 Figure 2.3 Reaction Vessel 24 Figure 2.4 Rotaflo TF6/24 Reaction Vessel 24 Figure 2.5 Silica Ampoule 26 Figure 2.6 Ampoule Breaker 26 Figure 2.7 Ampoule Breaker in use 26 Figure 2.8 Conductivity Cells 28 Figure 2.9 Infrared Gas Cell 31 Figure 2.10 Disc Press 33 Plate 2.2 Disc Press 33 Plate 2.3A Isolation Cell (Assembled View) 35 Plate 2.3B Isolation Cell (Exploded View) 36 Plate 2.4 Isolation Cell 37 Plate 2.5A Low Temperature Cell (Assembled View) 38 Plate 2.5B Low Temperature Cell (Exploded View) 39 Figure 2.11 Low Temperature Cell 40 Figure 2.12 Silica nmr tubes 43 Plate 2.6 Organometallic compounds in liquid HC1 44 Spectrum 2.1 Bis(it-cyclopentadienyldicarbonyl iron(l)) 58 Spectrum 2.2 Bi s(n-cyclopen tadi enyldic arbony1 iron(l)) 58 Spectrum 2.3 Bis(ic-cyclopentadienyldicarbonyl iron(l)) 59 Spectrum 2.4 Bis(it-cyclopentadienyldicarbonyl iron(l)) 59 Spectrum 2.5 Bis (ir-cyc lopentadieny ldicarbony 1 iron(l)) (Photolysis intermediate) 60 Spectrum 2.6 Tetrakis(rc-cyclopentadienylcarbonyl 'iron(l)) 60 Figure 3.1 Conductimetric titration of Bis(ic-cyclopentad- ienyldicarbonyl iron(l)) with Boron trichloride 65 Spectrum 3.1 ic-cyclopentadienyldicarbonyl iron-(j.- hydrogen n-cyclopentadienyldicarbonyl iron tetrachloroborate 68a Spectrum 3.2 ir-cyclopentadienyldicarbonyl iron-u-hydrogen rt-cyclopentadienyldicarbonyi iron hexafluorophosphate 68a Spectrum 3.3 n-cyclopentadienyltricarbonyl iron(II) hexafluorophosphate 68b + Structures I-VIII Structures of the [ (ir-C5H5)Fe(C0)2]2 X cations (X - H, CI, Brand I). 71 Figure 3.2 Decomposition of Tt-cyclopentadienyldi- carbonyl iron-|i-hydrogen it-cyclopentadienyldi- carbonyl iron hexafluorophosphate 72 Figure 4.1 Conductimetric titration of n-cyclopentadienyl- dicarbonyl iron chloride with boron trichloride 86 Spectrum 4.1 ir-cyclopentadienyldicarbonyl iron-|i- chloro n-cyclopentadienyldicarbonyl iron hexafluorophosphate 86 Spectrum 4.2 u-cyclopentadienyldicarbonyl iron(ll) chloride in sulphuric acid 91 Spectrum 4.3 ic-cyclopentadienyldicarbonyl iron(ll) bromide in sulphuric acid 92 Spectrum 4.4 n-cyclopentadienyldicarbonyl iron (II) iodide in sulphuric acid 93a Spectrum 4.5 K-cyclopentadienyltricarbonyl iron(II) tetrachloroborate 93b Figure 5.1 Conductimetric titration of Tetrakis (n-cyclopentadienylcarbonyl iron(l)) with boron trichloride Spectrum 5.1 Tetralcis (n-cyclopentadienylcarbonyl iron(l)) dihydrogen Tetrachloroborate 103a Spectrum 5.2 Tetrakis(n-cyclopentadienylcarbonyl iron(l)) bis(boron trichloride) Spectrum 5.3 Tetrakis(ir-cyclopentadienylcarbonyl iron(l)) hexafluorophosphate 111b Spectrum 5.4 Tetrakisdr-cyclopentadienylcarbonyl iron(l)) tribromide 111b Spectrum 5.5 TetrakisCn-cyclopentadienylcarbonyl iron(I)) heptaiodide Spectrum 6.1 it-cyclopentadienyldicarbonyl iron-u- chloro Tt-cyclopentadienyldicarbonyl iron hexafluorophosphate 123 Spectrum 6.2 u-cyclopentadienyldicarbonyl iron-|i-chloro it-cyclopentadienyldicarbonyl iron hexafluoro- phosphate 124 Spectrum 6.3 ic-cyclopentadienyldicarbonyl iron-u-bromo n-cyclopentadienyl dicarbonyl iron hexafluoro• phosphate 125 Spectrum 6.4 Tt-cyclopentadienyldicarbonyl iron-u-bromo it-cyclopentadienyl dicarbonyl iron hexafluoro- phosphate 126 Spectrum 6.5 n-cyclopentadienyldicarbonyl iron-u-iodo n-cyclopentadienyl dicarbonyl iron hexafluoro• phosphate 127 Spectrum 6.6 Tt-cyclopentadienyldicarbonyl iron-u-iodo u-cyclopentadienyldicarbonyl iron hexafluoro- phosphate 128 Spectrum 6.7 n-cyclopentadienyldicarbonyl iron-u-chloro Tt-cyclopentadienyldicarbonyl iron hexafluoro- phosphate 133 Spectrum 6.8 Thermal decomposition product of 7t-cyclopentadienyldicarbonyl iron-u-chloro Tt-cyclopentadienyl dicarbonyl iron hexafluoro- phosphate 133 Spectrum 6.9 Tt-cyclopentadienyldicarbonyl iron-u-bromo-it- cyclopentadienyl dicarbonyl iron hexafluoro- phosphate 134 Spectrum 6.10 Thermal decomposition product of Tt-cyclopentad- ienyl dicarbonyl iron-u-bromo Tt-cyclopentadienyl dicarbonyl iron hexafluorophosphate 134 Spectrum 6.11 Tt-cyclopentadienyldicarbonyl iron-u-iodo Tt-cyclopentadienyl dicarbonyl iron hexafluoro- phosphate 135 Spectrum 6.12 Thermal decomposition product of Tt-cyclopentad• ienyl dicarbonyl iron-u-iodo Tt-cyclopentadienyl dicarbonyl iron hexafluorophosphate 135 Figure 7.1 Basic processes in electron Spectroscopy 142 Figure 7.2 Photo ionisation of an electrical insulator 144 Figure 7.3 Electron relaxation 145 Spectrum 7.1 Bis(Tt-cyclopentadienyldicarbonyl iron(l)) 160 Spectrum 7.2 Tt-cyclopentadienyldicarbonyl iron(ll) chloride 161 Spectrum 7.3 Tt-cyclopentadienyldicarbonyl iron(ll) iodide 162 Spectrum 7.4 Tt-cyclopentadienyldicarbonyl iron-u-chloro- Tt-cyclopentadienyldicarbonyl iron hexafluoro- phosphate 163 Spectrum 7.5 Tt-cyclopentadienyldicarbonyl iron-u-bromo Tt-cyclopentadienyl dicarbonyl iron hexafluoro- phosphate 164 Spectrum 7.6 Tt-cyclopentadienyldicarbonyl iron-u-iodo Tt-cyclopentadienyldicarbonyl