Microscale Inorganic Chemistry

Zvi Szafran is the author of Microscale Inorganic Chemistry: A Comprehensive Laboratory Experience, published by Wiley. Ronald M. Pike is the author of Microscale Inorganic Chemistry: A Comprehensive Laboratory Experience, published by Wiley.

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, (NH4)2[BeF4] 164

Part B Synthesis of Ammonium Tetrafluoroborate, NH4[BF4] 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(NO3)2·H2O 209

Part B Synthesis of Co(mimt)2(NO3)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 CuCl2·2DMSO 220

Part B Preparation of PdCl2·2DMSO 221

Part C Preparation of RuCl2·4DMSO 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 Δ0 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 FeCl3 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(PPh3)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-C8H12PtCl2 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 SO2 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-C5H5)Fe(CO)2]2 325

Part B Variable Temperature 13C NMR lnvestigation of [η5-C5H5)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