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Studies Into the Effects of Hexa-Hapto Spectator Ligands on the Chemistry of Ruthenium

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Studies Into the Effects of Hexa-Hapto Spectator Ligands on the Chemistry of Ruthenium Studies into the Effects of Hexa-hapto Spectator Ligands on the Chemistry of Ruthenium A thesis presented to the University of London in partial fulfilment of the requirements for the degree of Doctor of Philosophy. Jonathan W. Steed. UCL UNIVERSITY COLLEGE LONDON, 1993. ProQuest Number: 10046152 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest 10046152 Published by ProQuest LLC(2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code. Microform Edition © ProQuest LLC. ProQuest LLC 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346 To my mother, who brought me unscathed through the first eighteen years of my life and little damaged thereafter, and to Coreena, of course. ABSTRACT This thesis describes the results of investigations into the chemistry of ruthenium complexes of hexa-hapto spectator ligands. Two specific systems have been examined. Chapters 2 - 5 describe aspects of the chemistry of the ruthenium(IV) chloride bridged compound [ {Ru(T|^:T|^-CioHi6)Cl(p-Cl) which contains the r|^:r|^-Z?w(allyl) ligand 2,7-dimethylocta-2,6-diene-l,8-diyl, derived from the ruthenium trichloride mediated dimérisation of isoprene. In Chapters 6 and 7 the reactivity of arenes and cyclohexadienes is examined in ruthenium complexes of the polyaromatic T|^-spectator [2.2]paracyclophane. Chapter 1 offers a general introduction to arene and allyl transition metal chemistry and attempts to place the results reported herein into a wider context. In Chapter 2 the reactions of the 6z^(allyl)ruthenium(IV) chloride bridged dimer [{Ru(Ti^:T|^-CioHi6)Cl(p-Cl) with amines and polypyridines are examined. Bridge cleaved amine adducts of formulae [Ru(T|^:'n^-CioHi6)Cl2L] or [{Ru('n^Ti^-CioHi6)Cl2}2(M'-L)] (L = PhNHj, o-pda, p-pda) are reported and the diastereoisomerism of the binuclear compounds examined. The mononuclear chelate compounds [Ru(il^:T|^-CioHig)Cl(L- L)][BFJ (L-L = 2,2’-diaminodiphenyl, 2,2’-bipyridyl, 1,10-phenanthroline) and [Ru(T|^:T|^- CioHi6)(terpy)] [BFJ 2 are formed from treatment of the starting material with Ag[BFJ and the appropriate ligand. Chapter 3 reports a number of carboxylato compounds of ruthenium(IV). These products occur as either 1 : 1 bidentate chelates [Ru(rj^:Tl^-CioHi6)Cl(02CR)] (R = Me, carboxylato / , , CH2F, CH2CI) or 1 : 2, monodentat^ aqua complexes [Ru('n^:'n^-CioHi6)(0 2 CR)2(OH2)] (R = CH2CI, CHjF, CHClj, CHFj, CCI3, CF3). The electronic properties of the carboxylato ligand are found to be crucial to the product stoichiometry. The analogous thiocarboxylato compounds [Ru('n^:'q^-CioHi6)Cl(OSCR)] (R = Me, Ph, ^ u ) exhibit bidentate coordination and exist as two alternative geometric isomers with the sulphur located either axially or equatorially. In the case where R = Me coordination is found to proceed via a two step process involving the monodentate thioacetic acid adduct [Ru(t|^ ti^- CioHi6)Cl2{S(OH)CMe}]. The related nitrato compounds [Ru(il^:'n^-CioHi@)Cl(N 0 3 )] and [Ru(T|^:T|^-CioHig)(N0 3 )2] are also reported. In the latter case the "semi-chelating" nitrato ligands readily become monodentate in the presence of two electron ligands to give adducts [Ru('n^:'n^-CioHi6)(N0 3 )2L] (L = CO, py). Chapter 4 reports a range of 2-pyridinol and pyridine-2-thiol compounds of ruthenium(IV) of form [Ru(T|^:T|^-CioHi6)a(pyrX)] (X = O, S) and related species. These compounds all exhibit axial and equatorial geometrical isomerism and a method based on NMR spectroscopy is described for distinguishing between the two forms. In Chapter 5 a range of bi- and trinuclear compounds of ruthenium(IV) are described and their inherent diastereoisomerism studied. The bridge-cleaved adducts [{Ru(T|^:Tl^-CioHi6)Cl2}2(|i-pyz)] and [{Ru(n^:T|^-CioHJCl 2}n(li-tra)] (n = 1, 2, 3) are reported along with the thiocyanato, carboxylato and nicotinato bridged compounds [{Ru(li':il'-C,oH,«)Cl(n-SCN)}j, [{Ru(n':n'-C.oHi«)Cl)#-0,R)] (R = C^, QHj) and [Ru2(T,'m'-QoH,«)A(n.NC;H,CO^]. In Chapter 6 the single nucleophilic addition reactions of simple anions N' (N = H, CN, OMe, Me) to unsymmetrical Z?w(arene)ruthenium(II) compounds [Ru(T|^-arene)(r|®- [2.2]paracyclophane)]^^ (arene = CgHg, p-MeC 6H4CHMe2, l,4-(CHMe2)2C6H4, CgMeg, CigHig) are examined. It is found that the cyclophane acts as a non-innocent spectator ligand, directing nucleophiles onto other arenes coordinated to the same metal centre to give the cyclohexadienyl compounds [Ru(T|^-[2.2]paracyclophane)(T^^-CgR^N)]^. Chapter 7 describes the extension of the work reported in Chapter 6 to double nucleophilic addition reactions to give ruthenium(O) compounds of general form [Ru(il^- [2.2]paracyclophane)('n'^-diene)]. The reactivity of these Ru(0) species towards H[BF 4] is examined resulting in a range of novel agostic compounds. Mechanistic aspects are investigated by a range of deuteriation studies. Finally, Chapter 8 offers some conclusions on what has been learned about the effects the two spectator ligands studied have on the chemistry of ruthenium. CONTENTS Abstract 3 Table of Contents 5 Acknowledgements 9 Abbreviations 10 Chapter 1; Introduction. 11 1.1 Motivations for the Present Work 12 1.2 Ti**-Arene Ligands 16 12.1 Properties and Bonding in Arene Transition Metal Complexes 16 12.2 Synthesis of Arene Transition Metal Complexes 19 12.3 Piano Stool Complexes of Ruthenium 21 Incorporating -Arene Spectator Ligands 1.3 T|®-Dienyl and rj^-Diene Complexes 25 13.1 Reactivity of Bis(arene)lron Complexes 25 1.3.2 Nucleophilic Addition to Bis(arene)Ruthenium Complexes 29 13.3 Charge and Orbital Control in Nucleophilic Addition Reactions 29 1.4 Ti^-Allyl Complexes 32 1.4.1 Simple Allyl Transition Metal Complexes 32 1.4.2 Reactions of Simple Transition Metal Compounds with Olefins 35 1.4.3 Reactions ofBis(allyl)Ruthenium Complexes 39 1.5 Other ri*^-Complexes 41 13.1 Cyclic Trienes and Tetraenes 41 13.2 Polyaromatic Bridging Ligands 43 13.3 Heteroatom -Donors 46 Chapter 2: Complexes of with N-donor Ligands 48 2.1 Introduction 49 2.2 Reactions with Amines 50 22.1 Reaction with Aniline 50 22.2 Reactions with 12- and 1,4-Diaminobenzene 51 22.3 Reactions with Other Potentially Bidentate Amine Ligands 57 2.3 Reactions with Oligopyridines 61 23.1 Synthesis of Chelate Complexes 61 23.2 Reactions to form Aqua Complexes 66 2.4 Experimental 67 Chanter 3: Mono- and Bidentate Carboxylato Complexes of Ruthenium(IV) 89 3.1 Introduction 90 3.2 Reactions with Acetate and Trifluoroacetate Anions 90 3.3 The Cross-over Between Mono- and Bidentate Coordination 96 3.4 X-ray Crystal Structure Determinations of Representative Compounds 99 3.5 Conclusions 100 3.6 Further Aqua Complexes of Ruthenium(IV) 101 3.6.1 ^-Diketonate Complexes 101 3.6.2 Reactions of [Ru('\^:'rf .’if -Cj2Hj8)CIJ 102 3.6.3 Attempted Oxidations 103 3.7 Reactions with Thiocarboxylic Acids 105 3.8 Synthesis and Structures of Nitrato Complexes 107 3.9 Experimental 113 Chapter 4; Geometrical Isomerism in Hvdroxvnvridinate and Pvridinethiolate Complexes of Ruthenium(IV) 142 4.1 Introduction 143 4.2 Reaction with 2-Hydroxypyridines 144 42.1 Reaction with 2-Hydroxypyridine 144 42.2 Reactions with 6-Substituted 2-Hydroxypyridines 146 42.3 Other OJSl-Donor Complexes Exhibiting Isomerism 149 4.3 Reaction with Pyridine-2-thiols 151 4.4 Factors Affecting Isomer Ratios 153 4.5 X-ray Crystal Structure Determinations of Representative Compounds 154 4.6 Conclusions 156 4.7 Experimental 156 Chanter 5: Bi- and Trinuclear Complexes of RutheniumdV) 172 5.1 Introduction 173 5.2 Bridge Cleavage Reactions 173 5 2.1 Reaction with Pyrazene 173 5 2 2 Reaction with 1,3,5-Triazine 178 52.3 Synthesis and Electrochemistry of Mixed Valence Compounds 180 5.3 Reaction with Silver Thiocyanate 181 5.4 Binuclear Carboxylato Bridged Complexes 187 5.4.1 Reaction with Oxalate Ions 187 5.4.2 Reaction with Malonate Ions 190 5.4.3 X-ray Crystal Structure Determination 191 5.5 Reactions with Nicotinic Acids 192 5.6 Experimental 197 Chapter 6: Single Nucleophilic Addition Reactions of (Arene)(r2.21Paracvclophane)Ruthenium(Il) Complexes 221 6.1 Introduction 222 6.2 Reactions of the (Benzene)([2.2]Paracyclophane)Ruthenium(U) Cation 223 6.3 Nucleophilic Additions to Alkylated Arenes 227 6.3.1 Addition to the ([2.2]Paracyclophane)(p-Cymene)Ruthenium(II) Cation 227 63.2 Addition to the ([2.2IParacyclophane) (Hexamethylbenzene)Ruthenium(II) Cation 231 6.3.3 Addition to the Bis([2.2]Paracyclophane)Ruthenium(II) Cation 232 6.4 Experimental 235 Chapter 7: Svnthesis and Reactivitv of Diene Complexes of Ruthenium(O) 245 7.1 Introduction 246 7.2 Double Nucleophilic Addition Reactions of Hydride 246 72.1 Re-examination of the Hydride Reduction of [Ru(rf-Ci^i 6)(^^-C^ea)P'*’ 246 72.2 Regioselectivity of the Hydride Reduction of [Ru(rf-Cj(iHjg)(r\^-C(fI^)f* 251 72.3 Action of Hydride upon Other [Ru(J\^-Ci^i^)(i\^-arene)Complexes 253 7.3 Attempted Synthesis of Substituted (Diene)Ruthenium(O) Complexes 257 7.4 Protonation of Ruthenium(O) Complexes 260 7.4.1 Protonation of [Ru(if-CjfjHj^)(r(^- 5 ,6 - C ^ e ^ 2)] 260 7.4.2 Protonation of [Ru(V(-Ci^i^)(vf-3, 6 - C ^ e ^ 2)l 265 7.4.3 Synthesis of Additional Agostic Cyclohexenyl Compounds 272 7.5 Experimental 276 Chapter 8: Overview and Conclusions
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