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ARENE RUTHENIUM CHEMISTRY by Richard Simon Bates Thesis

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ARENE RUTHENIUM CHEMISTRY by Richard Simon Bates Thesis ARENE RUTHENIUM CHEMISTRY by Richard Simon Bates Thesis submitted to the University of Nottingham for the Degree of Doctor of Philosophy. (MAY 1990) ACKNOWLEDGEMENTS First of all I would like to thank my supervisor Dr. Tony Wright for all his encouragement and enthusium throughout my PhD. I must also thank the technical staff, especially Ian Marshall and Mark Guyler for nmr experiments, Mike Cooper and Tony Hollingworth for mass spectrometry analysis, Tony Buckland and Ron Cartwright for making and repairing items of glassware, Mike Begley for help with solving crystal structures and Bob Waring and Jim Gamble for helping the laboratory running smoothly. However, the helpfulness and friendliness of the backroom team Edith, Chris, Jack, Clarice, Margaret Barnes, Linda and Margaret should also be noted for making the last three years so enjoyable. Good wishes and thanks also go to the students in B9a, past and present, who helped create such a good working environment during my time at Nottingham, Shakher Puntambekar, Kirsty Clode, John Stinchcombe, Rob Winder, Paul Smith, Simon Lyons, but most of all to Ian Beaumont and Simon Harrison who amongst their crimes have been so useful in the preparation of this manuscript. I now thank all members of my family for their support and understanding over the years. Oh yes, cheers SERC for financial support. CHAPTER ONE : INTRODUCTION Section 1: Introduction. 1.1 : Preparations of arene ruthenium complexes. 2 1.1.1 : Diene route. 2 1.1.2 : Fischer-Hafner. 4 1.1.3 Metal vapour. 11 Section 1.2 : Chemistry of [(arene)RuC12]2 and its derivatives. 14 1.2.1 : Neutral derivatives. 14 1.2.1.1 : Simple bridge cleavage. 14 1.2.1.2 : Bidentate coordinated 1igands. 15 1.2.1.3 : Arene ruthenium carboxylate complexes. 17 1.2.1.4 : Arene ruthenium alkyl derivatives. 21 1.2.1.5 : Hydrido arene ruthenium complexes. 28 1.2.1.6 : C-H bond activation and cyclometallated arene ruthenium complexes. 34 1.2.1.7 : Preparation of arene ruthenium(O) complexes from [(arene)RuC12]z. 38 1.2.1.8 : Arene ligand exchange. 41 1.2.2 : Ionic derivatives. 42 1.2.2.1 : Simple bridge cleavage. 42 1.2.2.2 : Conversion of half sandwich complexes. 42 1.2.2.3 : Preparation of tris ligated dications and cyclophane chemistry. 45 1.2.2.4 : The [(arene)Ru 9Cl)3Ru(arene)]' cation system. 54 1.2.2.5 : Reactivity of the [(arene)Ru(1/-C1)3Ru(arene)]+ cation system. 56 1.2.2.6 : Hydroxy and alkoxide arene ruthenium complexes. 59 1.2.2.6.1 : Hydroxide complexes. 59 1.2.2.6.2 : Alkoxide complexes. 61 1.2.2.7 : The anionic arene ruthenium chloro complex [(C6H6)RuCl3]-. 63 Section 1.3 X-ray crystal structure data. 63 CHAPTER TWO Section 2.1 : Arene ruthenium zero valent complexes. 67 Section 2.2 : Arene ruthenium bis(ethylene) system. 72 Section 2.3 : Mechanism. 86 Section 2.4 : Reaction studies of arene ruthenium bis(ethylene) system. 87 2.4.1 : Protonation studies of the arene ruthenium bis(e thylene) system. 88 2.4.1.1 Protonation of (C6H6)Ru(C2H4)2 followed by 'H nmr spectroscopy. 88 2.4.1.2 : Protonation of (C6H6)Ru(CZH4)2 followed by 13C nmr spectroscopy. 95 2.4.1.3 : Protonation of (MeC6H4CHMe2)Ru (C2H4)2 followed by 'H nmr spectroscopy. 97 2.4.2 : Related experiments. 100 2.4.3 : Nucleophilic Substitution. 113 Section 2.5 : Scheme of compounds in chapter 2.115 Section 2.6 : General experimental. 116 2.6.1 : Experimental. 118 CHAPTER THREE Section 3.1 : Synthesis of a reactive arene ruthenium intermediate. 124 Section 3.2 : Investigation of the reactivity of the tetrahydrofuran complex. 126 3.2.1 : Oxidative addition. 127 3.2.2 : Source of naked ruthenium. 133 3.2.3 Reaction with PPh3.140 3.2.3.1 : Reactivity of the PPh3 complex. 143 Section 3.3 : Structure of arene ruthenium moiety complexes of chapter 2 and 3.144 Section 3.4 : Reaction scheme of complexes prepared in chapter 3.147 Section 3.5 : Experimental. 148 CHAPTER FOUR Section 4.1 : Ruthenium clusters. 152 4.1.1 : Cluster reactions utilising 152 simple arene ruthenium derivatives. 4.1.2 : Ultrasound as a synthetic tool for cluster reactions. 155 4.1.3 : Arene ruthenium selenium 155 cluster chemistry. 4.1.4 : Arene ruthenium hydride 158 cluster chemistry. 4.1.5 : Ruthenium carbonyl cluster 172 chemistry. 4.1.6 : Arene ruthenium sulphido cluster chemistry. 175 Section 4.2 : Reaction scheme of clusters synthesised in chapter 4.179 Section 4.3 : Experimental 180 CHAPTER FIVE Section 5.1 : Arene ruthenium complexes containing nitrogen ligands. 184 5.1.1 : Preparation of neutral arene ruthenium primary amine complexes. 184 5.1.2 : Preparation of cationic primary amine complexes. 186 5.1.3 : Investigation of alternative amine type ligands. 187 5.1.4 : Mechanism. 187 5.1.5 : Chemistry of primary amine complexes. 193 5.1.5.1 : Cation formation. 193 5.1.5.2 : Deprotonation and reduction. 195 5.1.6 : Conclusions. 197 Section 5.2.1 : Preparation of arene ruthenium azido complexes. 198 5.2.2 : Structure of [(MeC6H4CHMez)RuCl(N3)]Z. 200 5.2.3 : Mechanism. 207 5.2.4 : Investigation of the chemistry of the azide dimer. 211 5.2.4.1 : Thermolysis. 211 5.2.4.2 : Hydride reaction. 212 5.2.4.3 : Cation formation. 213 5.2.4.4 : Simple cleavage reactions. 214 Section 5.3 : Reaction schemes of complexes found in chapter 5.217 5.3.1 : Reaction scheme of amine complexes. 217 5.3.2 : Reaction scheme of azide related complexes. 218 Section 5.4 : Experimental. 219 CHAPTER SIX Section 6.1 : Conclusions and future work. 233 APPENDIX Ultrasound in synthesis. 241 Mechanisms of the chemical effects of ultrasound. 241 Nucleation of cavitation. 242 Cavitation in a homogeneous liquid. 243 Cavitation at surfaces. 244 Reactor designs. 248 REFERENCES 250 Abstract This thesis describes the synthesis and reactivity studies of new arene-ruthenium(II) and arene-ruthenium(O) complexes. Ultrasound has been investigated as an alternative energy source, with the overall aim of synthesising arene ruthenium clusters. Chapter 1 gives an introduction and summary of the known arene ruthenium chemistry reported to date. Chapter 2 reports the synthesis of (CGH6)Ru(C2H4)2 and (MeC6H4CHMe2)Ru(C2H4)2. Low temperature protonation studies generated (C6H6)Ru(H)(CZH4)2' and (MeC6H4CHMe2)Ru(H)(C2H4)7ý. These are observed by 1H nmr spectroscopy to undergo two dynamic processes, rotation of the ethylene ligands and an exchange between the hydride and the hydrogens of the ethylenes. On protonation with trifluoroacetic acid (C6H6)Ru(02CCF3)2 has been shown to be the final product. Nucleophilic substitution investigations of the bis(ethylene) complexes has determined that the arene is more labile than the coordinated ethylene. Chapter 3 reports the generation of a reactive intermediate, [(MeC6H4CHMez)Ru(THF)2]", and the reactions it undergoes. The synthesis and stereochemistry of the new complexes [(MeC6H4CHMe2)RuBr(C3H5)] and Ru(H)[(C6H40) (OPh)2][P(OPh)3]3 are reported. Chapter 4 describes the successful synthesis of the project goal, with the formation of the trimer [(MeC. H., CHMe2)3Ru3Se, and the tetra nuclear species _1` [(MeC6H4CHMe2)4Ru4H4]2'. Electrochemistry shows both complexes undergo two, one-electron reversible reductions to generate their neutral analogues. Ru3(CO)12 was formed when arene ruthenium carbonyl clusters were sought. Chapter 5 reports the formation and reactivity of arene ruthenium complexes containing nitrogen based ligands. The half sandwich complexes, (arene)RuCl2(NH2R) (arene = C6H6, R= Et, CMe, C6H4Me; McC6H4CHMe2, R= CMe3) and (C. H6)RuCl(NHZCGH4Me)Z' have been synthesised in good yield. However, these complexes are not synthetically useful as substrates for cluster synthesis, although (C6H6)RuC12(NH2CMe3) can be converted to the mixed ethoxide-halide dimer, [(C6H6)Ru(OEt)]2Cl`. Me3SiN3 on reaction with [(MeC6H4CHMe2)RuC12]2 affords [(MeC6H4CHMe2)RuCl(N3)]Z. An X-ray crystal structure determination of this complex showed the nitrogens bridging the two ruthenium atoms are pyramidal rather than the expected planar in geometry. [(MeC6H4CHMe2)RuCl(N3)]2 undergoes chloride loss to form the triply bridged dimer, [(MeCGH4CHMe2)RuCl(N3)z]', and bridge cleavage to form [(MeC, H4CHMe2)RuCl(N3)PPh3]. The latter complex is believed to undergo disproportionation in solution. Conclusions and future directions of the project are discussed in chapter. 6. The appendix provides a discussion of ultrasound. * proposed structure. Abbreviations DMSO dimethylsulfoxide Pyz pyrazine THE tetrahydrofuran acac acetylacetonate COT cyclooctatetraene py pyridine cp cyclopentadiene cp* pentamethylcyclopentadiene HMB hexamethylbenzene CYM cymene Bz benzene TFA trifluoroacetic acid dppen cis Ph2PCH=CHPPh2 ))) ultrasound anal. analysis calc. calculated FAB Fast Atom Bombardment amu atomic mass unit * postulated structure COD cyclooctadiene solv solvent He methyl Et ethyl Ph phenyl Bu butyl CHAPTER ONE Chapter 1 1. Introduction A more diverse group of arene complexes exists for ruthenium than any other metal. The diversity stems from the stability of the arene-metal bond and the ready availability of highly reactive arene containing starting materials. Arene ruthenium complexes play an increasingly important role in organometallic chemistry. Along with osmium, these arene complexes appear to be good starting materials for access to reactive arene metal hydrides or 16 electron metal(O) intermediates that have been used for carbon-hydrogen bond activation. From classic organometallic arene ruthenium chemistry an area relating to the search for "New Materials" has developed. Contributions to the chemistry of cyclophanes (compounds which are potential precursors of organometallic polymers) has occurred. Cocondensation of arene with ruthenium vapours has recently allowed access to new types of arene ruthenium metal complexes and clusters.
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