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PEROXO COMPLEXES of the EARLY TRANSITION METALS By PEROXO COMPLEXES OF THE EARLY TRANSITION METALS by Andrew Charles Dengel B.Sc. A.R.C.S A Thesis presented in partial fulfilment of the requirements for the Degree of Doctor of Philosophy of the University of London Inorganic Chemistry Laboratories Department of Chemistry Imperial College London December 1987 abstract The work described in this thesis concerns the peroxo chemistry of the transition metals in Groups IVa-VIa. As well as the preparation, characterisation and study of the chemistry of new peroxo complexes of the second and third row members of these groups, the work includes study of the aqueous peroxo chemistry and some known peroxo complexes of the metals. The work has been undertaken both from an academic viewpoint and to investigate existing and new methods for the recovery, extraction and separation of the early second and third row metals; the latter process is notoriously difficult due to the effects of the lanthanide contraction. 2 New carboxylato n -peroxo complexes K2[M0(02)2(L)J .2H20 (M = Mo, W; L = glycollate, tartrate, malate, gluconate), K2[Mo0(02)2(L)].2H20 (L = tartronate, quinate), and A[M0(0)(CH0)).4H04 22 24 426 2 (A = K, NH.4 ; M = Mo, W; C 4 H 2 0 o = tetraionised tartrate) have been prepared, and char- acterised using infrared, Raman, and 13C and 95Mo n.m.r. spectroscopy. X-Ray crystal structures are presented for K2CMo0(02)2(glyc)].2H20 and K [Mo 0 (0o),(C H 0 ) ].4H_0. The new organic-soluble peroxo complex 4 i c 2 4 4 2 b 2 (Ph,P)„CMo(MO ) (ox)] is shown to oxidise activated alcohols to carbonyl compounds. Studies on the aqueous peroxo chemistry of molybdenum and tungsten include investigation of the action of hydrogen peroxide on tungsten carbide and molybdenum carbide, and study of the known ^M203*02*4^2~ = Mo< w * sPecies. New organic-soluble complexes *Ph4P*2^M2°3*°2*4^ = M°* an<S *®U4N*2^M°2°3*°2*4^ 316 used *or the oxidation of various alcohols to carbonyl compounds and the epoxidation of alkenes. 1 2 New Group Va carboxylato n -peroxo complexes )3(L )] (H = Nb, Ta ; L = tartrate, glycollate, citrate), l<3[Nb(02)3(malate)], KtM(0 ) (dipicolinate)(H 0)3.HO (M = Nb. Ta), and Ke[Mo(0o)e(CfHo0e)] c c c Z o Z 2 b 4 Z b (M = Nb, Ta) have been prepared and characterised by infrared, Raman and 13C n.m.r. spectroscopy. The aqueous peroxo chemistry of niobium and tantalum has been studied using Raman spectroscopy, and the 2 - vibrational spectra of the [Nb(0_)F_32 5 anion re-investigated in detail. 2 New Group IVa n -peroxo complexes K [M( M ox) 3.2H 0 and 2 2 2 2 K2 ^ ° 2 * 2 * c*trate^ *H2° = Zr’ have also been prepared, and characterised by infrared and Raman spectroscopy. 2 U SLJtf-CQNTENTS Page ABSTRACT i LIST OF CONTENTS 3 LIST OF TABLES 11 LIST OF FIGURES 13 ABBREVIATIONS AND SYMBOLS 16 ACKNOWLEDGEMENTS 18 DEDICATION 19 CHAPTER ONE : THE R2 -PER0X0 LIGAND AND ITS COMPLEXATION WITH 20 TRANSITION METALS Section 1.1 HISTORICAL AND GENERAL BACKGROUND 20 Section 1.2 CLASSIFICATION OF DIOXYGEN COMPLEXES 24 Section 1.3 THE q2-PEROXO LIGAND 26 1.3.1 Electronic Structure and Bonding Theory 26 1.3.2 Spectroscopic Properties 28 Section 1.4 FORMATION OF n2“PEROXO COMPLEXES OF TRANSITION 29 METALS Section 1.5 REACTIVITY OF n2-PEROXO COMPLEXES OF TRANSITION 31 METALS Section 1.6 APPLICATION OF PEROXO CHEMISTRY TO THE SEPARATION 33 AND EXTRACTION OF EARLY TRANSITION METALS 3 Ptflt CHAPTER TWO : PEROXO COMPLEXES OF MOLYBDENUM(VI) AND TUNGSTEN(VI) 35 Section 2.1 INTRODUCTION 35 2.1.1 General Background 35 2.1.2 Simple Peroxo and Oxoperoxo Complexes of 37 Molybdenum(VI) and Tungsten(VI) 2.1.3 Heteroligand Peroxo Complexes of Molybdenum(VI) 44 and Tungsten(VI) (a) Haloperoxo Complexes 44 (b) Peroxo Complexes Containing Ligands Derived 47 from Carboxylic Acids and Nitrogen Bases (c) Miscellaneous Heteroligand Peroxo Complexes 54 2.1.4 Reactivity and Applications of Peroxo Complexes 56 of Molybdenum(VI) and Tungsten(VI) 2.1.4.1 Reactivity 56 (a) General Reactivity 56 (b) Stoichiometric Oxidation 57 (c) Catalytic Oxidation 65 2.1.4.2 Applications of PeroxoChemistry to the 70 Extraction and Separation of Molybdenum and Tungsten 4 Section 2.2 CARBOXYLATO PEROXO COMPLEXES OF MOLYBDENUM(VI) 73 AND TUNGSTEN(VI) 2.2.1 Preparation of 1:1 Metal:Carboxylate Peroxo 73 Complexes 2.2.1.1 Introduction 73 2.2.1.2 Formation of Complexes 74 (a) Oxalato Peroxo Complexes 74 (b) Citrato Peroxo Complexes 78 (c) New Carboxylato Peroxo Complexes 78 2.2.1.3 Structure and Vibrational Spectra of 85 CM0(02)2(L)]2" (M = Mo, W); The X-Ray Crystal Structure of K2[Mo0(02)2(glyc)].2H20 2.2.1.4 Use of 95Mo and 13C N.M.R. Spectroscopy to 97 2- Investigate the Structure of [MO(02>2(L)3 Species in Solution 2.2.2 Preparation of 2:1 Metal:Tartrate Peroxo 106 Complexes; The X-Ray Crystal Structure of K4CMo202(02)^(C^H206)].4H20 2.2.3 Reactivity of Carboxylato Peroxo Complexes 114 of MolybdenumtVI) (a) Preparation of Organic-Soluble Carboxylato 114 Peroxo Complexes (b) Attempted Reactions with SO,,2 and C0„2 115 (c) Oxidative Reactivity Towards Alkenes and 117 Alcohols 5 JEgflg Section 2.2.4 Differences Between the Carboxylato Peroxo 122 Chemistry of MolybdenumtVI) and TungstentVI): Separational Possibilities (a) The 1:1 M:Glycollate System (M = Mo, W) 124 (b) The 2:1 M:Tartrate System (M = Mo, W) 125 Section 2.3 0X0PER0X0 AND PEROXO MOLYBDATES(VI) AND 128 TUNGSTATES(VI) IN THE SOLID STATE AND AQUEOUS SOLUTION 2.3.1 Vibrational Spectra of .2H20 128 (M = Mo, W) : 2H- and 180- Substitution Studies (a) Comparison of Calculated and Experimental 129 18 Shifts in M^O Frequencies upon 0-Substitution 2 (b) Effect of H-Substitution upon the Vibrational 132 Spectra 2.3.2 The Caesium Molybdate - Hydrogen Peroxide 132 System 2.3.3 Vibrational Spectra of Known Oxoperoxo 136 Molybdates(VI) (a) <n V 8CMo 1()022(02 ) 12].16H20 '37 (b) (NH 4 ) 4 [Mo 3 07 ( 0Z ) 4 3.2HZ 0 138 (c) K6[Mo7022(02>2].8H20 138 2.3.4 Oxidative Reactivity of 139 Species (M = Mo, W) 6 P»g« Section 2.3.4 (a) Nature of the species Responsible for Molyb- 139 date- and Tungstate-Catalysed Oxidation of Alkenes and Alcohols by H„0„,2 2 (b) Preparation of Organic-Soluble Salts of 142 tM2°3(02,*IH20,2l2' <M * Mo. W) (cl Use of (Ph4P)2tM203 C02> + 3 (H = Ho, H) and H 3 (Bu ^N)2[Mo 203 (02)^] as Stoichiometric Oxidants Section 2.4 THE ACTION OF HYDROGEN PEROXIDE ON TUNGSTEN 153 CARBIDE AND MOLYBDENUM CARBIDE 2.4.1 Introduction 153 2.4.2 The Action of Hydrogen Peroxide on Tungsten 156 Carbide (a) Recovery of Tungsten as CaWO^ 157 (b) Raman Spectrum of the WC/H202/0xalic Acid 158 Solution (c) Attempted Isolation of PeroxotungstatetVI) 165 Species Present in the WC/H„0„/0xalic2 2 Acid Solution 2.4.3 The Action of Hydrogen Peroxide on Molybdenum 167 Carbide 2.4.4 Conclusions 170 7 flfll Section 2.5 FLUORO CARBOXYLATO PEROXO COMPLEXES OF 171 MOLYBDENUMSVI) AND URANIUM(VI) 2.5.1 Introduction 171 2.5.2 Attempted Preparation of Fluoro Carboxylato 172 Peroxo Complexes of Molybdenum (VI) and Uranium(VI) Section 2.6 EXPERIMENTAL 174 CHAPTER THREE : PEROXO COMPLEXES OF THE GROUP Va AND IVa 210 TRANSITION METALS Section 3.1 INTRODUCTION 210 3.1.1 General Background 210 3.1.2 Peroxo Complexes of Group Va 211 3.1.2.1 Vanadium 211 3.1.2.2 Niobium and Tantalum 215 (a) Aqueous Peroxo Chemistry 216 (b) Heteroligand Peroxo Complexes 219 (c) Reactivity and Applications 227 3.1.3 Peroxo Complexes of Group IVa 229 3.1.3.1 Titanium 229 3.1.3.2 Zirconium and Hafnium 234 8 Plfll Section 3.2 CARBOXYLATO PEROXO COMPLEXES OF NIOBIUM(V) 240 AND TANTALUM(V) 3.2.1 Introduction 240 3.2.2 Preparation of Starting Materials 241 3.2.3 Preparation of New 1:1 Metal:Carboxylate 242 Peroxo Complexes 3.2.3.1 Formation of Complexes 242 3.2.3.2 Vibrational and 13C N.M.R. Spectra of the 247 Complexes 3.2.4 Preparation of New 2:1 Metal:Tartrate 251 Peroxo Complexes Section 3.3 AQUEOUS PEROXO CHEMISTRY OF NIOBIUM AND TANTALUM 253 3.3.1 Raman Spectra of Peroxidic Solutions of 253 Niobium(V) and Tantalum(V) 3.3.2 The Action of Hydrogen Peroxide on Niobium 256 Carbide and Tantalum Carbide Section 3.4 VIBRATIONAL SPECTRA OF THE CNb(0o)Fe]2"2 5 ANION 258 3.4.1 Introduction 256 3.4.2 The Vibrational Spectra of [Nb(0n)F_]2”Z 5 259 (a) K2[Nb(02)F5].H20 259 (b) "Na2tNb(02)F5r 267 (C) <Ph4P)2CNb(02)F5] 269 9 Section 3.5 PREPARATION OF NEW CARBOXYLATO PEROXO COMPLEXES 270 OF ZIRCONIUM(IV) AND HAFNIUM(IV) 3.5.1 Introduction 270 3.5.2 Formation of Complexes 271 3.5.3 Vibrational Spectra of the Complexes 272 Section 3.6 MISCELLANEOUS TITANIUM(IV) AND VANADIUM(V) PEROXO 275 CHEMISTRY 3.6.1 AColorimetric Method for the Distinction 275 between Coordinated and Perhydrate Peroxide using Titanium(IV) 2 3.6.2 The Effect of H-Substitution on the 277 Vibrational Spectra of (NH ) HCV 0 (0 ) ].H 0 Section 3.7 EXPERIMENTAL 279 APPENDIX : GENERAL EXPERIMENTAL 291 Physical Measurements Reagents Analyses REFERENCES 293 PUBLICATIONS 317 10 L IS T OF TABLES I»bl« 1.1 Structural Classification of Dioxygen Complexes 25 2.1 Vibrational Data for 1:1 Metal:Carboxylate Molybdenum(VI) 89 and Tungsten(VI) Carboxylato Peroxo Complexes 2.2 Bond Lengths (A) and Angles (°) in K2CMo0(02)2(glyc) ].2^0 96 95 2.3 Mo N.M.R.
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