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 xviiIntroduction 1–3A. A Brief History of Inorganic Chemistry 1B. The Microscale Approach 2C. A Word to the Student 3Chapter 1 Safety in the Laboratory 5–171.A General Safety Rules 51.A.1 Introduction 51.A.2 Before the Laboratory 61.A.3 Safety Rules in the Laboratory 61.B Planning for Chemicaly Safety 81.B.1 Introduction 81.B.2 Use of MSD Sheets 81.B.3 The Merck Index 121.B.4 Compressed Gas Cylinders and Lecture Bottles 131.B.5 Fire Safety 16Chapter 2 Laboratory Equipment 19–292.A Glassware 192.B Other Locker Equipment 212.C Measuring Quantities of Chemicals 222.C.1 Weighing 222.C.2 Liquid Volumes 222.D Heating Methods 252.D.1 The Microburner 252.D.2 Steam Bath 252.D.3 Oil Baths 252.D.4 Infrared Lamp 262.D.5 Sand Bath or Aluminum Block with Magnetic Stirring Hot Plate 262.E Stirring 272.F Reflux and Distillation 27Chapter 3 Writing Laboratory Reports 31–353.A Introduction 313.B Maintenance of the Laboratory Notebook 313.C The Laboratory Report 343.D Proper Citation and Plagiarism 35Chapter 4 Literature Searching and the Inorganic Literature 37–474.A Literature Searching 374.A.1 Chemical Abstracts Method 37Searching a Topic in Chemical Abstracts 38Use of the Formula Index 38Use of the General Subject Index 40CAS Online 40Advantages and Disadvatages of Chemical Abstracts 404.A.2 Use of the Science Citation Index 41Searching Using the Printed Science Citation Index 41Searching Using the Compact Disc Science Citation Index 42Searching Using the Citation Index 42Advantages and Disadvatages of the Science Citation Index 444.A.3 Comparison of the Two Methods 444.B The Inorganic Chemical Literature 444.B.1 Introduction 444.B.2 Purely Inorganic Journals 444.B.3 General Coverage Journals 454.B.4 Review Journals and Monographs Covering Inorganic Chemistry 454.B.5 Major Comprehensive Books on Inorganic Chemistry 46Chapter 5 Inorganic Microscale Laboratory Techniques 49–1055.A Microscale Determination of Magnetic Susceptibility 495.A.1 Introduction 495.A.2 Measurement of Magnetic Susceptibility 505.A.3 Calculation of Magnetic Moment from Magnetic Susceptibility 525.A.4 Operation of the Evans–Johnson Matthey Balance for Solids 545.A.5 Operation for Liquids and Solutions 555.A.6 Determining Magnetic Susceptibility by NMR Spectroscopy 565.B Thermal Analysis 575.B.1 Introduction 575.B.2 Differential Scanning Calorimetry and Differential Thermal Analysis 575.B.3 Thermogravimetric Analysis 585.B.4 Variables in Thermal Analysis 585.B.5 Analysis of the Thermogram 595.B.6 Theoretical Aspects 605.B.7 Applications 615.C Vacuum and Inert Atmosphere Techniques 62Introduction 625.C.1 Purging with an Inert Gas 625.C.2 Use of Manifold for Inert Gas or Vacuum 64Rough Pump 64Cold Trap 64Manifold 65Multiple Vacuum Lines in Series 65Use and Operation of Manifolds 655.C.3 Cannula Techniques 665.D Crystallization Techniques 675.D.1 Introduction 675.D.2 Crystallization from Solution 675.D.3 Isolation of Crystalline Products (Suction Filtration) 695.D.4 The Craig Tube Method 695.D.5 Recrystallization Pipet 705.D.6 Removal of Suspended Particles from Solution 715.D.7 Washing of the Collected Crystals 715.D.8 Decolorization 725.D.9 Drying Techniques 735.E Determination of Melting Points 745.E.1 Introduction 745.E.2 Theory 745.E.3 Mixture Melting Point Determination 755.E.4 Correcting Melting Points 765.E.5 Determination of the Melting Point Range 775.E.6 Melting Point Apparatus 78The Thiele Tube 78The Mel-Temp Apparatus 78The Fisher–Johns Apparatus 78The Thomas–Hoover Apparatus 815.F Concentration of Solutions 815.F.1 Introduction 815.F.2 Evaporation Techniques 815.F.3 Removal of Solvent Under Reduced Pressure 815.G Chromatography 825.G.1 Introduction 825.G.2 Thin-Layer Chromatography 845.G.3 Gas Chromatography: Introduction 86Components of the Gas Chromatograph 875.G.4 Liquid Chromatography 89Ion and Ion Exchange Chromatography 89High-Performance Liquid Chromatography 905.H Sublimation 925.H.1 Introduction 925.H.2 Theory 935.H.3 Sublimation Technique 935.I Solvent Extraction 945.I.1 Introduction 945.I.2 Theory 945.I.3 Extraction Procedures: Simple Extraction 97Use of the Separatory Funnel 97Pasteur Filter Pipet Extractions 995.I.4 Continuous Extraction 1005.I.5 Drying of the Wet Organic Layer 1005.I.6 Drying of Organic Solvents 1015.J Conductivity Measurements 1025.J.1 Introduction 1025.J.2 Experimental Procedure 1045.J.3 Non-Aqueous Solutions 105Chapter 6 Spectroscopy 107–1466.A Introduction 1076.A.1 Spectrometer Components 1086.B Visible Spectroscopy 1096.B.1 Introduction and Theory 1096.B.2 The Visible Spectrum 1106.B.3 Molar Absorbance and Color 1116.B.4 Size of the Crystal Field Splitting 1126.B.5 Energy Level Diagrams l126.C Infrared Spectroscopy 1146.C.1 Introduction 1146.C.2 Sample Handling 1156.C.3 Bond Vibrations 1l66.C.4 Vibrational Modes 1196.C.5 Inorganic Functional Groups 1216.C.6 Synergistic Effects 1216.C.7 Interpretation of IR Spectra 1226.C.8 Fourier Transform lnfrared 1236.D Nuclear Magnetic Resonance Spectroscopy 1256.D.1 Introduction 1256.D.2 Sample Preparation 1286.D.3 Reference Materials 1296.D.4 The Chemical Shift 1296.D.5 Integration 1316.D.6 Spin–Spin Coupling 1326.D.7 13C-NMR Spectroscopy 1336.D.8 Quadrupolar Nuclei 1366.D.9 The Coupling Constant 1366.D.10 Interpretation of Inorganic Spectra 1376.D.11 Spectral Collapse l386.D.12 Decoupling 1396.D.13 Identification of Isomers 1396.E Atomic Absorption Spectroscopy 1416.E.1 Introduction 1416.E.2 Theory 1416.E.3 The Instrument 142The Flame 142The Nebulizer Burner System 142The Light Source 144The Monochromator 144The Detector 1446.E.4 Measurement of Concentration 1446.E.5 Other Considerations 145Chapter 7 Chemistry of the Main Group Elements 147–215Experiment 1 Preparation of Sodium Amide 148Experiment 2 Synthesis and Thermal Analysis of the Group 2 (IIA)Metal Oxalate Hydrates 152Experiment 3 Atomic Absorption Analysis of Magnesium and Calcium 155Experiment 4 Preparation of Trialkoxyborates 158Part A Preparation of Tri-n-propylborate 160Part B Preparation of a Poly(vinylalcohol)–Borate Copolymer 161Experiment 5 Synthesis of Tetrafluoroberyllate andTetrafluoroborate Complexes 163Part A Synthesis of Ammonium Tetrafluoroberyllate, (NH4)2[BeF4] 164Part B Synthesis of Ammonium Tetrafluoroborate, NH4[BF4] 165Experiment 6 Synthesis of Dichlorophenylborane 167Experiment 7 Synthesis and Reactions of Carboranes 170Part A Preparation of Potassium Dodecahydro-7-8-dicarba-nido-undecarborate(1-), a Carborane Anion 172Part B Preparation of 3-[η5-Cyclopentadienyl)-1,2-dicarba-3-cobalta-closo-dodecaborane(11), a Metal Carborane 173Experiment 8 Silicone Polymers: Preparation of Bouncing Putty 176Experiment 9 The Oxidation States of Tin 181Part A Preparation of Tin(IV) Iodide 183Part B Preparation of Tin(II) Iodide 184Experiment 10 Relative Stabilities of Tin(IV) and Lead(IV) 186Part A Preparation of Ammonium Hexachlorostannate(IV) 186Part B Preparation of Ammonium Hexachloroplumbate(IV) 187Experiment 11 Preparation of Substituted 1,2,3,4-Thiatriazoles 189Part A Preparation of 5-Anilino-1,2,3,4-thiatriazole 190Part B Preparation of 5-Amino-1,2,3,4-thiatriazole 191Experiment 12 Synthesis of Hexakis(4-nitrophenoxy) cyclotriphosphazene 193Part A Preparation of Potassium 4-Nitrophenoxide 194Part B Preparation of Hexakis(4-nitrophenoxy) cyclotriphosphazene 195Experiment 13 Synthesis of Ammonium Phosphoramidate 197Experiment 14 Preparation of an Explosive: Nitrogen Triiodide Ammoniate 199Experiment 15 Synthesis of Trichlorodiphenylantimony[V) Hydrate 201Experiment 16 Preparation of Tetrathionate 204Part A Determination of Reaction Quantities 205Part B Quantitative Preparation of Sodium Tetrathionate 206Experiment 17 Thione Complexes of Cobalt(II) Nitrate Hexahydrate 207Part A Synthesis of Co(mimt)4(NO3)2·H2O 209Part B Synthesis of Co(mimt)2(NO3)2 209Experiment 18 Positive Oxidation States of Iodine: Preparation of Dipyridineiodine(I) Nitrate 210Experiment 19 Synthesis of Interhalogens: Iodine Trichloride 213Chapter 8 Chemistry of the Transition Metals 217Experiment 20 Metal Complexes of Dimethyl Sulfoxide 218Part A Preparation of CuCl2·2DMSO 220Part B Preparation of PdCl2·2DMSO 221Part C Preparation of RuCl2·4DMSO 221Experin1ent 21 Preparation of trans-Dichlorotetrapyridinerhodium(III) Chloride 222Experiment 22 Synthesis of Metal Acetylacetonates 224Part A Preparation of Tris(2,4-pentanedionato) chromium(III) 226Part B Preparation of Tris(2,4-pentanedionato) manganese(III) 227Experiment 23 Gas Chromatographic Analysis of Brominated Tris(2,4-pentanedionato) chromium(III) 229Experiment 24 Determination of Magnetic Moments in Metal–Metal Bonded Complexes 231Part A Synthesis of Rhodium(II) Acetate Ethanolate 232Part B Synthesis of Copper(II) Acetate Monohydrate 234Experiment 25 Multiply Bonded Species: Preparation of Tetrabutylammonium Octachlorodirhenate(III) 235Experiment 26 Geometic Isomerism 239Part A Synthesis of trans-Dichlorobis(ethylenediamine)cobalt(III) Chloride 241Part B Synthesis of cis-Dichlorobis(ethylenediamine)cobalt(III) Chloride 242Experiment 27 Optical Isomers: Separation of an Optical Isomer ofcis-Dichlorobis (ethylenediamine)cobalt(III) Chloride 243Experiment 28 Ion Exchange Separation of the Oxidation States of Vanadium 246Experiment 29 Determination of Δ0 in Cr(III) Complexes 248Experiment 30 Preparation and Study of a Cobalt(II) Oxygen Adduct Complex 252Part A Preparation of N,N' -Bis(salicylaldehyde) ethylenediimine, salenH2 254Part B Preparation of Co(salen) 254Part C Determination of Oxygen Absorption by Co(salen) 256Part D Reaction of Oxygen Adduct with Chloroform 257Experiment 31 Preparation of Dichloro-1,3-bis[diphenylphosphino)propanenickel(II) 257Experiment 32 Preparation of Iron(II) Chloride (Use of FeCl3 as a Friedel–Crafts Chlorination Source) 260Experiment 33 Reaction of Cr(III) with a Multidentate Ligand: A Kinetics Experiment 263Experiment 34 Organometallic Compounds and Catalysis: Synthesis and Use of Wilkinson’s Catalyst 271Part A Synthesis of RhCl(PPh3)3, Wilkinson’s Catalyst 276Part B Substitution of the Chloro Ligand in Wilkinson’s Catalyst 277Part C Reaction of Wilkinson’s Catalyst with Aldehydes 278Part D Reaction of Wilkinson’s Catalyst with Ethylene 279Part E Absorption of Hydrogen by Wilkinson’s Catalyst 279Part F Catalytic Hydrogenation of Olefins in the Presence of Wilkinson’s Catalyst 281Experiment 35 Synthesis and Reactions of Cobalt Phenanthroline Complexes 282Part A Preparation of Tris(1, 10-phenanthroline) cobalt(II) Bromide 283Part A (Alternate): Preparation of Tris(1, 10-phenanthroline) cobalt(II) Antimonyl-d-tartrate 284Part B Preparation of Tris(1, 10-phenanthroline) cobalt(III) Tetrafluoroborate 285Part C Preparation of Tris(1, 10-phenanthroline-5,6-quinone)cobalt(III) Hexafluorophosphate 286Part D Isolation of 1, 10-phenanthroline-5,6-quinone 287Experiment 36 Preparation of Tetrakis(triphenylphosphine)platinum(0) 288Experiment 37 Platinum(II) Complexes––the Trans Effect 290Part A Preparation of cis-Dichloro(dipyridine) platinum(II) 291Part B Preparation of trans-Dichloro(dipyridine) platinum(II) 291Chapter 9 Chemistry of Organometallic and Related Compounds 295Experiment 38 Organoplatinum[II) Complexes: Preparation of η4-C8H12PtCl2 296Experiment 39 NMR Investigation of Molecular Fluxionality: Synthesis of Allylpalladium Complexes 298Experiment 40 Preparation and Use of Ferrocene 302Part A Preparation of Cyclopentadiene 304Part B Preparation of Ferrocene 305Part C Acetylation of Ferrocene 307Part D HPLC Analysis of the Acetylation Reaction 309Experiment 41 Preparation of Organopalladium Complexes 310Part A Preparation of Dichloro-bis-(benzonitrile) palladium(II) 311Part B Preparation of Di-µ-chlorodichlorodiethylenedipalladium(II) 312Experiment 42 Synthesis of Metal Carbonyls 313Part A Preparation of trans-Chlorocarbonylbis­ (triphenylphosphine)rhodium(I) 315Part B Preparation of mer-Carbonyltrichlorobis ­(triphenylphosphine)rhodium(III) 316Part C Synthesis of the SO2 Adduct of trans­ Chlorocarbonylbis(triphenylphosphine)rhodium(I) 317Experiment 43 Sunlight Photochemistry: Preparation of Dicarbonyl(η5-methylcyclopentadienyl)triphenylphosphinemanganese (0) 318Experiment 44 Synthesis of Metal Nitrosyl Complexes 320Part A Preparation of Trichloronitrosyl-bis(triphenylphosphine)ruthenium(II) 321Part B Preparation of Dinitrosylbis(triphenylphosphine)ruthenium(– II) 323Experiment 45 13C NMR Analysis of Cyclopentadienylirondicarbonyl Dimer 324Part A Preparation of [(η5-C5H5)Fe(CO)2]2 325Part B Variable Temperature 13C NMR lnvestigation of [η5-C5H5)Fe(CO)2]2 327Chapter 10 Bioinorganic Chemistry 329Experiment 46 Synthesis of Palladium Nucleosides 330Part A Preparation of cis-[Dichlorobis(inosine) palladium(II)] 331Part B Preparation of cis-[Bis(lnosinato) palladium(II)] 332Part C Preparation of trans-[Bis(inosinato) palladium(II)] 333Experiment 47 Metal Complexes of Saccharin 334Part A Preparation of Tetraaqua-bis(o-sulfobenzoimido)copper(II) 336Part B Preparation of Tetraaqua-bis(o-sulfobenzoimido)cobalt(II) 336Experiment 48 Synthesis of cis-Diamminedihaloplatinum(II) Compounds 337Part A Preparation of cis-Diamminediiodoplatinum(II) 338Part B Preparation of cis-diamminedichloroplatinum(II), Cisplatin 339Experiment 49 Preparation of Copper Glycine Complexes 341Part A Preparation of cis-Bis(glycinato) copper(II) Monohydrate 342Part B Preparation of trans-Bis(glycinato) copper(II) 342Appendix A Safety Data for Common Solvents 345Appendix B List of Common Acids and Bases 347Appendix C Table of Reagents and Selected Solvents Used in Experiments 349Appendix D Table of Instrumental Techniques Used in Experiments 353Appendix E Companies and Addresses 355Index 359