Advanced Practical Inorganic and Metalorganic Chemistry

by Errington; R. John

• ISBN13: 9780751402254
• ISBN10: 0751402257
• Format: Nonspecific Binding
• Copyright: 1997-07-03
• Publisher: CRC Press

Summary

While the boundaries between the areas of chemistry traditionally labeled as inorganic, organic and physical are gradually diffusing, the practical techniques adopted by workers in each of these areas are often radically different. The breadth and variety of research classed as "inorganic chemistry" is readily apparent from an inspection of some of the leading international journals, and can be quite daunting for newcomers to this domain who are likely to have only limited experience of the methodologies involved. This book has therefore been written to provide guidance for those unfamiliar with the techniques most often encountered in synthetic inorganic / metalorganic chemistry, with an emphasis on procedures for handling air-sensitive compounds. One chapter is devoted to more specialized techniques such as metal vapor synthesis, and a review of preparative methods for a selection of starting materials is included as an aid to those planning research projects. While this book is aimed primarily at postgraduate and advanced undergraduate students involved in inorganic research projects, synthetic organic chemists and industrial chemists will also find much useful information within its pages. Similarly, it serves as a useful reference source for materials and polymer scientists who wish to take advantage of recent progress in precursor synthesis and catalyst development.

Table of Contents

Preface	xii
1 General introduction	1	(2)
2 Preliminaries	3	(22)
2.1 The laboratory	3	(5)
2.1.1 Bench space	3	(2)
2.1.2 Fume cupboards	5	(1)
2.1.3 Apparatus and glassware	5	(1)
2.1.4 Solvent stills	5	(1)
2.1.5 Procuring chemicals and equipment	6	(1)
2.1.6 Carrying out reactions	6	(1)
2.1.7 Cleaning and drying glassware	6	(1)
2.1.8 Disposal of residues	7	(1)
2.1.9 Using departmental facilities	8	(1)
2.2 The literature	8	(9)
2.2.1 Finding your way through the chemical literature	9	(4)
2.2.2 Keeping up to date	13	(1)
2.2.3 Searching for specific information	14	(2)
2.2.4 Organizing the information	16	(1)
2.3 Keeping records	17	(4)
2.3.1 The lab notebook	17	(3)
2.3.2 Recording and filing data	20	(1)
2.4 Safety	21	(4)
2.4.1 Legal aspects	21	(1)
2.4.2 Responsibilities	22	(1)
2.4.3 General behaviour and awareness	22	(1)
2.4.4 Risk assessment	22	(3)
3 Bench-top techniques	25	(28)
3.1 Introduction to inert atmosphere techniques	25	(1)
3.2 The inert-gas vacuum double manifold	26	(7)
3.2.1 Design	26	(2)
3.2.2 Setting up the manifold	28	(2)
3.2.3 The vacuum pump	30	(1)
3.2.4 The inert gas supply	31	(1)
3.2.5 Purification columns	31	(1)
3.2.6 Initial setup	32	(1)
3.3 Schlenk techniques	33	(6)
3.3.1 Principles involved	33	(1)
3.3.2 Reaction flasks	34	(1)
3.3.3 Ground-glass joints and taps	34	(1)
3.3.4 Greasing ground glass	34	(3)
3.3.5 Greaseless taps and joints	37	(2)
3.3.6 Attaching flexible hoses to glassware	39	(1)
3.4 Syringe and cannula techniques	39	(10)
3.4.1 Using cannulae	39	(2)
3.4.2 Filtration with a filter stick	41	(2)
3.4.3 Syringes	43	(6)
3.5 Apparatus	49	(4)
4 Glove boxes	53	(14)
4.1 Introduction	53	(1)
4.2 General features	53	(8)
4.2.1 The box	54	(2)
4.2.2 Maintaining an inert atmosphere	56	(4)
4.2.3 Pressure control	60	(1)
4.3 Maintenance and use	61	(6)
4.3.1 Preparing to use the dry box	61	(1)
4.3.2 Taking items in	62	(1)
4.3.3 Working inside the box	63	(1)
4.3.4 Taking items out	64	(1)
4.3.5 Useful items	64	(1)
4.3.6 General maintenance	65	(2)
5 Operations on the high-vacuum line	67	(25)
5.1 Introduction	67	(1)
5.2 The high-vacuum line	67	(5)
5.2.1 The pumping station	69	(1)
5.2.2 Pressure gauges	70	(6)
5.2.3 The vacuum manifold	76	(1)
5.2.4 The work station	77	(5)
5.3 Manipulating volatile materials	82	(4)
5.3.1 Volatile liquids	82	(1)
5.3.2 Condensable gases	83	(1)
5.3.3 Fractionation trains	83	(1)
5.3.4 Slush baths	83	(1)
5.3.5 Quantitative gas measurements	84	(2)
5.4 High-vacuum pumps	86	(3)
5.4.1 Diffusion pumps	86	(1)
5.4.2 Turbomolecular pumps	87	(2)
5.5 Alternative designs of high-vacuum lines	89	(3)
6 Solvents and reagents	92	(31)
6.1 Introduction	92	(1)
6.2 Purifying and storing solvents	92	(9)
6.2.1 General considerations	92	(1)
6.2.2 Drying	93	(4)
6.2.3 Solvents	97	(4)
6.3 Design and maintenance of solvent stills	101	(6)
6.3.1 Design considerations	101	(2)
6.3.2 Maintenance and use	103	(4)
6.4 Reagents	107	(7)
6.4.1 Halogenation	107	(1)
6.4.2 Ligand metathesis/exchange	108	(1)
6.4.3 Alkylation	109	(2)
6.4.4 Reduction	111	(1)
6.4.5 Oxidation	112	(1)
6.4.6 Deprotonation	113	(1)
6.5 Gases	114	(9)
6.5.1 Gas cylinders	115	(4)
6.5.2 Generation of reagent gases	119	(2)
6.5.3 Purification of reagent gases	121	(2)
7 Carrying out reactions in solution	123	(19)
7.1 Introduction and general considerations	123	(1)
7.2 Measuring out reagents	124	(7)
7.2.1 Solids	124	(2)
7.2.2 Liquids	126	(1)
7.2.3 Gases	127	(4)
7.3 Transferring solvents	131	(1)
7.4 Mixing	131	(4)
7.4.1 Magnetic stirring	132	(1)
7.4.2 Mechanical stirring	132	(3)
7.5 Heating	135	(4)
7.5.1 Heating under reflux	135	(3)
7.5.2 Heating for short times	138	(1)
7.6 Cooling	139	(1)
7.7 Monitoring the reaction	140	(2)
8 Reaction work-up	142	(29)
8.1 Introduction	142	(1)
8.2 Isolating products	142	(7)
8.2.1 Filtration	143	(3)
8.2.2 Removing solvents	146	(1)
8.2.3 Precipitation	147	(1)
8.2.4 Trituration	148	(1)
8.2.5 Soxhlet extraction	148	(1)
8.3 Purifying products	149	(16)
8.3.1 Recrystallization	150	(3)
8.3.2 Distillation	153	(7)
8.3.3 Sublimation	160	(3)
8.3.4 Chromatography	163	(2)
8.4 Storing products	165	(6)
8.4.1 Ampoules	166	(5)
9 Reactions between a solid and a gas	171	(6)
9.1 Introduction	171	(1)
9.2 Designing apparatus	171	(3)
9.2.1 Horizontal reactors	171	(2)
9.2.2 Vertical reactors	173	(1)
9.3 Procedure	174	(3)
10 Reactions between solids	177	(6)
10.1 Introduction	177	(1)
10.2 General considerations	177	(1)
10.3 Choice of container	178	(1)
10.4 Typical procedures	179	(4)
10.4.1 Glass containers	179	(2)
10.4.2 Metal containers	181	(2)
11 Product characterization	183	(36)
11.1 Introduction	183	(1)
11.2 Spectroscopic techniques	183	(21)
11.2.1 NMR spectroscopy	184	(13)
11.2.2 Vibrational spectroscopy	197	(6)
11.2.3 Electronic spectroscopy	203	(1)
11.3 Mass spectrometry	204	(2)
11.4 Elemental microanalysis and molecular weight determinations	206	(4)
11.4.1 CHN combustion analysis	207	(1)
11.4.2 Determination of elements other than C, H and N	208	(1)
11.4.3 Molecular weight determination	208	(2)
11.5 Growing crystals for single-crystal X-ray diffraction	210	(2)
11.5.1 Slow evaporation	210	(1)
11.5.2 Vapour diffusion	211	(1)
11.5.3 Mounting crystals	212	(1)
11.6 Powder X-ray diffraction	212	(1)
11.7 Other techniques	213	(6)
11.7.1 Conductivity measurements	213	(2)
11.7.2 ESR spectroscopy	215	(1)
11.7.3 Mossbauer spectroscopy	216	(1)
11.7.4 Thermogravimetry	216	(1)
11.7.5 Magnetic measurements	216	(1)
11.7.6 Determination of melting point	216	(3)
12 Special techniques	219	(25)
12.1 Introduction	219	(1)
12.2 Electrochemical techniques	219	(4)
12.2.1 Cyclic voltammetry	219	(3)
12.2.2 Controlled potential electrolysis	222	(1)
12.3 Thermal analysis	223	(2)
12.3.1 Thermogravimetry	223	(1)
12.3.2 Differential thermal analysis and differential scanning calorimetry	223	(1)
12.3.3 Equipment	224	(1)
12.4 High pressure reactions	225	(4)
12.4.1 Glass reaction vessels	226	(1)
12.4.2 Metal reaction vessels	227	(2)
12.5 Photochemical reactions	229	(2)
12.6 Sonication	231	(2)
12.7 Microwave heating	233	(1)
12.8 Reactions in special solvents	234	(4)
12.8.1 Condensable gases	234	(1)
12.8.2 Super-critical fluids	235	(2)
12.8.3 Ambient temperature ionic liquids	237	(1)
12.9 Matrix isolation	238	(1)
12.10 Metal vapour synthesis	239	(5)
12.10.1 Heating options	239	(2)
12.10.2 Static reactors	241	(1)
12.10.3 Rotating reactors	242	(2)
13 Preparation of starting materials	244	(21)
13.1 Introduction	244	(1)
13.2 Halides and their simple derivatives	244	(6)
13.2.1 M(I) halides	245	(1)
13.2.2 M(II) halides	245	(2)
13.2.3 M(III) halides	247	(2)
13.2.4 M(IV) halides	249	(1)
13.2.5 M(V) halides	249	(1)
13.2.6 M(VI) halides	250	(1)
13.3 Amides	250	(1)
13.4 Alkoxides and related compounds	251	(2)
13.5 Oxo compounds	253	(2)
13.5.1 Oxohalides and related compounds	253	(1)
13.5.2 Oxometalates	254	(1)
13.6 Organoimido complexes	255	(1)
13.7 Carbonyls	256	(1)
13.8 Cyclopentadienyl complexes	257	(3)
13.9 Miscellaneous metal complexes	260	(1)
13.9.1 XXX-Diketonates and carboxylates	260	(1)
13.9.2 Thio and alkylthiolate complexes	260	(1)
13.9.3 Pd(0) and Pt(0) phosphine complexes	261	(1)
13.9.4 Complexes with weakly bound ligands	261	(1)
13.10 Ligands and reagents	261	(4)
13.10.1 Magnesium alkyls	261	(1)
13.10.2 Phosphorus compounds	262	(1)
13.10.3 Silicon and tin reagents	262	(1)
13.10.4 Miscellaneous compounds	263	(2)
Appendix A Health and safety information	265	(7)
Appendix B Deoxygenation columns	272	(2)
Appendix C Solvents	274	(3)
Appendix D NMR solvents	277	(4)
Appendix E Gases	281	(2)
Index	283