Microscale Inorganic Chemistry

This text is intended to provide students with instruction and valuable laboratory experience in the often neglected area of inorganic chemistry. Divided into four main parts, the book covers chemistry of the main group elements, chemistry of the transition metals, organometallic chemistry, and bioinorganic chemistry. Recognizing the high cost of materials, difficulties in waste disposal, and dangers of toxicity, the authors have adopted a ``microscale'' approach to experiments in the book, thereby also reducing the time students spend in preparation. With over 45 experiments, Microscale Inorganic Chemistry incorporates the use of a broad sampling of elements and also covers such topics as laboratory safety, equipment, report writing, and literature searching.

List of Tables xvii Introduction 1–3 A. A Brief History of Inorganic Chemistry 1 B. The Microscale Approach 2 C. A Word to the Student 3 Chapter 1 Safety in the Laboratory 5–17 1.A General Safety Rules 5 1.A.1 Introduction 5 1.A.2 Before the Laboratory 6 1.A.3 Safety Rules in the Laboratory 6 1.B Planning for Chemicaly Safety 8 1.B.1 Introduction 8 1.B.2 Use of MSD Sheets 8 1.B.3 The Merck Index 12 1.B.4 Compressed Gas Cylinders and Lecture Bottles 13 1.B.5 Fire Safety 16 Chapter 2 Laboratory Equipment 19–29 2.A Glassware 19 2.B Other Locker Equipment 21 2.C Measuring Quantities of Chemicals 22 2.C.1 Weighing 22 2.C.2 Liquid Volumes 22 2.D Heating Methods 25 2.D.1 The Microburner 25 2.D.2 Steam Bath 25 2.D.3 Oil Baths 25 2.D.4 Infrared Lamp 26 2.D.5 Sand Bath or Aluminum Block with Magnetic Stirring Hot Plate 26 2.E Stirring 27 2.F Reflux and Distillation 27 Chapter 3 Writing Laboratory Reports 31–35 3.A Introduction 31 3.B Maintenance of the Laboratory Notebook 31 3.C The Laboratory Report 34 3.D Proper Citation and Plagiarism 35 Chapter 4 Literature Searching and the Inorganic Literature 37–47 4.A Literature Searching 37 4.A.1 Chemical Abstracts Method 37 Searching a Topic in Chemical Abstracts 38 Use of the Formula Index 38 Use of the General Subject Index 40 CAS Online 40 Advantages and Disadvatages of Chemical Abstracts 40 4.A.2 Use of the Science Citation Index 41 Searching Using the Printed Science Citation Index 41 Searching Using the Compact Disc Science Citation Index 42 Searching Using the Citation Index 42 Advantages and Disadvatages of the Science Citation Index 44 4.A.3 Comparison of the Two Methods 44 4.B The Inorganic Chemical Literature 44 4.B.1 Introduction 44 4.B.2 Purely Inorganic Journals 44 4.B.3 General Coverage Journals 45 4.B.4 Review Journals and Monographs Covering Inorganic Chemistry 45 4.B.5 Major Comprehensive Books on Inorganic Chemistry 46 Chapter 5 Inorganic Microscale Laboratory Techniques 49–105 5.A Microscale Determination of Magnetic Susceptibility 49 5.A.1 Introduction 49 5.A.2 Measurement of Magnetic Susceptibility 50 5.A.3 Calculation of Magnetic Moment from Magnetic Susceptibility 52 5.A.4 Operation of the Evans–Johnson Matthey Balance for Solids 54 5.A.5 Operation for Liquids and Solutions 55 5.A.6 Determining Magnetic Susceptibility by NMR Spectroscopy 56 5.B Thermal Analysis 57 5.B.1 Introduction 57 5.B.2 Differential Scanning Calorimetry and Differential Thermal Analysis 57 5.B.3 Thermogravimetric Analysis 58 5.B.4 Variables in Thermal Analysis 58 5.B.5 Analysis of the Thermogram 59 5.B.6 Theoretical Aspects 60 5.B.7 Applications 61 5.C Vacuum and Inert Atmosphere Techniques 62 Introduction 62 5.C.1 Purging with an Inert Gas 62 5.C.2 Use of Manifold for Inert Gas or Vacuum 64 Rough Pump 64 Cold Trap 64 Manifold 65 Multiple Vacuum Lines in Series 65 Use and Operation of Manifolds 65 5.C.3 Cannula Techniques 66 5.D Crystallization Techniques 67 5.D.1 Introduction 67 5.D.2 Crystallization from Solution 67 5.D.3 Isolation of Crystalline Products (Suction Filtration) 69 5.D.4 The Craig Tube Method 69 5.D.5 Recrystallization Pipet 70 5.D.6 Removal of Suspended Particles from Solution 71 5.D.7 Washing of the Collected Crystals 71 5.D.8 Decolorization 72 5.D.9 Drying Techniques 73 5.E Determination of Melting Points 74 5.E.1 Introduction 74 5.E.2 Theory 74 5.E.3 Mixture Melting Point Determination 75 5.E.4 Correcting Melting Points 76 5.E.5 Determination of the Melting Point Range 77 5.E.6 Melting Point Apparatus 78 The Thiele Tube 78 The Mel-Temp Apparatus 78 The Fisher–Johns Apparatus 78 The Thomas–Hoover Apparatus 81 5.F Concentration of Solutions 81 5.F.1 Introduction 81 5.F.2 Evaporation Techniques 81 5.F.3 Removal of Solvent Under Reduced Pressure 81 5.G Chromatography 82 5.G.1 Introduction 82 5.G.2 Thin-Layer Chromatography 84 5.G.3 Gas Chromatography: Introduction 86 Components of the Gas Chromatograph 87 5.G.4 Liquid Chromatography 89 Ion and Ion Exchange Chromatography 89 High-Performance Liquid Chromatography 90 5.H Sublimation 92 5.H.1 Introduction 92 5.H.2 Theory 93 5.H.3 Sublimation Technique 93 5.I Solvent Extraction 94 5.I.1 Introduction 94 5.I.2 Theory 94 5.I.3 Extraction Procedures: Simple Extraction 97 Use of the Separatory Funnel 97 Pasteur Filter Pipet Extractions 99 5.I.4 Continuous Extraction 100 5.I.5 Drying of the Wet Organic Layer 100 5.I.6 Drying of Organic Solvents 101 5.J Conductivity Measurements 102 5.J.1 Introduction 102 5.J.2 Experimental Procedure 104 5.J.3 Non-Aqueous Solutions 105 Chapter 6 Spectroscopy 107–146 6.A Introduction 107 6.A.1 Spectrometer Components 108 6.B Visible Spectroscopy 109 6.B.1 Introduction and Theory 109 6.B.2 The Visible Spectrum 110 6.B.3 Molar Absorbance and Color 111 6.B.4 Size of the Crystal Field Splitting 112 6.B.5 Energy Level Diagrams l12 6.C Infrared Spectroscopy 114 6.C.1 Introduction 114 6.C.2 Sample Handling 115 6.C.3 Bond Vibrations 1l6 6.C.4 Vibrational Modes 119 6.C.5 Inorganic Functional Groups 121 6.C.6 Synergistic Effects 121 6.C.7 Interpretation of IR Spectra 122 6.C.8 Fourier Transform lnfrared 123 6.D Nuclear Magnetic Resonance Spectroscopy 125 6.D.1 Introduction 125 6.D.2 Sample Preparation 128 6.D.3 Reference Materials 129 6.D.4 The Chemical Shift 129 6.D.5 Integration 131 6.D.6 Spin–Spin Coupling 132 6.D.7 13C-NMR Spectroscopy 133 6.D.8 Quadrupolar Nuclei 136 6.D.9 The Coupling Constant 136 6.D.10 Interpretation of Inorganic Spectra 137 6.D.11 Spectral Collapse l38 6.D.12 Decoupling 139 6.D.13 Identification of Isomers 139 6.E Atomic Absorption Spectroscopy 141 6.E.1 Introduction 141 6.E.2 Theory 141 6.E.3 The Instrument 142 The Flame 142 The Nebulizer Burner System 142 The Light Source 144 The Monochromator 144 The Detector 144 6.E.4 Measurement of Concentration 144 6.E.5 Other Considerations 145 Chapter 7 Chemistry of the Main Group Elements 147–215 Experiment 1 Preparation of Sodium Amide 148 Experiment 2 Synthesis and Thermal Analysis of the Group 2 (IIA) Metal Oxalate Hydrates 152 Experiment 3 Atomic Absorption Analysis of Magnesium and Calcium 155 Experiment 4 Preparation of Trialkoxyborates 158 Part A Preparation of Tri-n-propylborate 160 Part B Preparation of a Poly(vinylalcohol)–Borate Copolymer 161 Experiment 5 Synthesis of Tetrafluoroberyllate and Tetrafluoroborate Complexes 163 Part A Synthesis of Ammonium Tetrafluoroberyllate, (NH 4 ) 2 [BeF 4 ] 164 Part B Synthesis of Ammonium Tetrafluoroborate, NH 4 [BF 4 ] 165 Experiment 6 Synthesis of Dichlorophenylborane 167 Experiment 7 Synthesis and Reactions of Carboranes 170 Part A Preparation of Potassium Dodecahydro-7-8-dicarba-nido-undecarborate(1-), a Carborane Anion 172 Part B Preparation of 3-[η5-Cyclopentadienyl)-1,2-dicarba-3-cobalta-closo-dodecaborane(11), a Metal Carborane 173 Experiment 8 Silicone Polymers: Preparation of Bouncing Putty 176 Experiment 9 The Oxidation States of Tin 181 Part A Preparation of Tin(IV) Iodide 183 Part B Preparation of Tin(II) Iodide 184 Experiment 10 Relative Stabilities of Tin(IV) and Lead(IV) 186 Part A Preparation of Ammonium Hexachlorostannate(IV) 186 Part B Preparation of Ammonium Hexachloroplumbate(IV) 187 Experiment 11 Preparation of Substituted 1,2,3,4-Thiatriazoles 189 Part A Preparation of 5-Anilino-1,2,3,4-thiatriazole 190 Part B Preparation of 5-Amino-1,2,3,4-thiatriazole 191 Experiment 12 Synthesis of Hexakis(4-nitrophenoxy) cyclotriphosphazene 193 Part A Preparation of Potassium 4-Nitrophenoxide 194 Part B Preparation of Hexakis(4-nitrophenoxy) cyclotriphosphazene 195 Experiment 13 Synthesis of Ammonium Phosphoramidate 197 Experiment 14 Preparation of an Explosive: Nitrogen Triiodide Ammoniate 199 Experiment 15 Synthesis of Trichlorodiphenylantimony[V) Hydrate 201 Experiment 16 Preparation of Tetrathionate 204 Part A Determination of Reaction Quantities 205 Part B Quantitative Preparation of Sodium Tetrathionate 206 Experiment 17 Thione Complexes of Cobalt(II) Nitrate Hexahydrate 207 Part A Synthesis of Co(mimt) 4 (NO 3 ) 2 ·H 2 O 209 Part B Synthesis of Co(mimt) 2 (NO 3 ) 2 209 Experiment 18 Positive Oxidation States of Iodine: Preparation of Dipyridineiodine(I) Nitrate 210 Experiment 19 Synthesis of Interhalogens: Iodine Trichloride 213 Chapter 8 Chemistry of the Transition Metals 217 Experiment 20 Metal Complexes of Dimethyl Sulfoxide 218 Part A Preparation of CuCl 2 ·2DMSO 220 Part B Preparation of PdCl 2 ·2DMSO 221 Part C Preparation of RuCl 2 ·4DMSO 221 Experin1ent 21 Preparation of trans-Dichlorotetrapyridinerhodium(III) Chloride 222 Experiment 22 Synthesis of Metal Acetylacetonates 224 Part A Preparation of Tris(2,4-pentanedionato) chromium(III) 226 Part B Preparation of Tris(2,4-pentanedionato) manganese(III) 227 Experiment 23 Gas Chromatographic Analysis of Brominated Tris(2,4-pentanedionato) chromium(III) 229 Experiment 24 Determination of Magnetic Moments in Metal–Metal Bonded Complexes 231 Part A Synthesis of Rhodium(II) Acetate Ethanolate 232 Part B Synthesis of Copper(II) Acetate Monohydrate 234 Experiment 25 Multiply Bonded Species: Preparation of Tetrabutylammonium Octachlorodirhenate(III) 235 Experiment 26 Geometic Isomerism 239 Part A Synthesis of trans-Dichlorobis(ethylenediamine)cobalt(III) Chloride 241 Part B Synthesis of cis-Dichlorobis(ethylenediamine)cobalt(III) Chloride 242 Experiment 27 Optical Isomers: Separation of an Optical Isomer of cis-Dichlorobis (ethylenediamine)cobalt(III) Chloride 243 Experiment 28 Ion Exchange Separation of the Oxidation States of Vanadium 246 Experiment 29 Determination of Δ 0 in Cr(III) Complexes 248 Experiment 30 Preparation and Study of a Cobalt(II) Oxygen Adduct Complex 252 Part A Preparation of N,N' -Bis(salicylaldehyde) ethylenediimine, salenH2 254 Part B Preparation of Co(salen) 254 Part C Determination of Oxygen Absorption by Co(salen) 256 Part D Reaction of Oxygen Adduct with Chloroform 257 Experiment 31 Preparation of Dichloro-1,3-bis[diphenylphosphino)propanenickel(II) 257 Experiment 32 Preparation of Iron(II) Chloride (Use of FeCl 3 as a Friedel–Crafts Chlorination Source) 260 Experiment 33 Reaction of Cr(III) with a Multidentate Ligand: A Kinetics Experiment 263 Experiment 34 Organometallic Compounds and Catalysis: Synthesis and Use of Wilkinson’s Catalyst 271 Part A Synthesis of RhCl(PPh 3 ) 3 , Wilkinson’s Catalyst 276 Part B Substitution of the Chloro Ligand in Wilkinson’s Catalyst 277 Part C Reaction of Wilkinson’s Catalyst with Aldehydes 278 Part D Reaction of Wilkinson’s Catalyst with Ethylene 279 Part E Absorption of Hydrogen by Wilkinson’s Catalyst 279 Part F Catalytic Hydrogenation of Olefins in the Presence of Wilkinson’s Catalyst 281 Experiment 35 Synthesis and Reactions of Cobalt Phenanthroline Complexes 282 Part A Preparation of Tris(1, 10-phenanthroline) cobalt(II) Bromide 283 Part A (Alternate): Preparation of Tris(1, 10-phenanthroline) cobalt(II) Antimonyl-d-tartrate 284 Part B Preparation of Tris(1, 10-phenanthroline) cobalt(III) Tetrafluoroborate 285 Part C Preparation of Tris(1, 10-phenanthroline-5,6-quinone)cobalt(III) Hexafluorophosphate 286 Part D Isolation of 1, 10-phenanthroline-5,6-quinone 287 Experiment 36 Preparation of Tetrakis(triphenylphosphine)platinum(0) 288 Experiment 37 Platinum(II) Complexes––the Trans Effect 290 Part A Preparation of cis-Dichloro(dipyridine) platinum(II) 291 Part B Preparation of trans-Dichloro(dipyridine) platinum(II) 291 Chapter 9 Chemistry of Organometallic and Related Compounds 295 Experiment 38 Organoplatinum[II) Complexes: Preparation of η4-C 8 H 12 PtCl 2 296 Experiment 39 NMR Investigation of Molecular Fluxionality: Synthesis of Allylpalladium Complexes 298 Experiment 40 Preparation and Use of Ferrocene 302 Part A Preparation of Cyclopentadiene 304 Part B Preparation of Ferrocene 305 Part C Acetylation of Ferrocene 307 Part D HPLC Analysis of the Acetylation Reaction 309 Experiment 41 Preparation of Organopalladium Complexes 310 Part A Preparation of Dichloro-bis-(benzonitrile) palladium(II) 311 Part B Preparation of Di-µ-chlorodichlorodiethylenedipalladium(II) 312 Experiment 42 Synthesis of Metal Carbonyls 313 Part A Preparation of trans-Chlorocarbonylbis­ (triphenylphosphine)rhodium(I) 315 Part B Preparation of mer-Carbonyltrichlorobis ­(triphenylphosphine)rhodium(III) 316 Part C Synthesis of the SO 2 Adduct of trans­ Chlorocarbonylbis(triphenylphosphine)rhodium(I) 317 Experiment 43 Sunlight Photochemistry: Preparation of Dicarbonyl(η5-methylcyclopentadienyl)triphenylphosphinemanganese (0) 318 Experiment 44 Synthesis of Metal Nitrosyl Complexes 320 Part A Preparation of Trichloronitrosyl-bis(triphenylphosphine)ruthenium(II) 321 Part B Preparation of Dinitrosylbis(triphenylphosphine)ruthenium(– II) 323 Experiment 45 13C NMR Analysis of Cyclopentadienylirondicarbonyl Dimer 324 Part A Preparation of [(η5-C 5 H 5 )Fe(CO) 2 ] 2 325 Part B Variable Temperature 13C NMR lnvestigation of [η5-C 5 H 5 )Fe(CO) 2 ] 2 327 Chapter 10 Bioinorganic Chemistry 329 Experiment 46 Synthesis of Palladium Nucleosides 330 Part A Preparation of cis-[Dichlorobis(inosine) palladium(II)] 331 Part B Preparation of cis-[Bis(lnosinato) palladium(II)] 332 Part C Preparation of trans-[Bis(inosinato) palladium(II)] 333 Experiment 47 Metal Complexes of Saccharin 334 Part A Preparation of Tetraaqua-bis(o-sulfobenzoimido)copper(II) 336 Part B Preparation of Tetraaqua-bis(o-sulfobenzoimido)cobalt(II) 336 Experiment 48 Synthesis of cis-Diamminedihaloplatinum(II) Compounds 337 Part A Preparation of cis-Diamminediiodoplatinum(II) 338 Part B Preparation of cis-diamminedichloroplatinum(II), Cisplatin 339 Experiment 49 Preparation of Copper Glycine Complexes 341 Part A Preparation of cis-Bis(glycinato) copper(II) Monohydrate 342 Part B Preparation of trans-Bis(glycinato) copper(II) 342 Appendix A Safety Data for Common Solvents 345 Appendix B List of Common Acids and Bases 347 Appendix C Table of Reagents and Selected Solvents Used in Experiments 349 Appendix D Table of Instrumental Techniques Used in Experiments 353 Appendix E Companies and Addresses 355 Index 359