Inorganic Experiments Edited by J. Derek Woollins

Weinheim • New York • Basel • Cambridge • Tokyo

Contents

1 Introduction 1

2 Introductory Experiments 5

2.1 Preparation and Investigation of Some Coordination Compounds 7 2.2 Gravimetric Analysis of Hexammine Nickel(n) Tetrafluoroborate, [Ni(NH3)6]

[BF4]2 10 2.3 Analysis of an Iron Oxalate Complex 14 2.4 Characterisation of a Copper Oxalate Complex, КаСий (C204)c • dH20 18 2.5 Vanadium Alum: An Experiment in Electrosynthesis 20 2.6 Ammonium Dichromate, Chromium(in) Oxide, Sodium Chromate and Potas­

sium Tetraperoxochromate(v) 22 2.7 Linkage Isomerism: An Infra-Red Study 26 2.8 Preparation and Complexation of Tris (3,5-dimethylpyrazoyl)hydroborate . . . . 28 2.9 Tetraiodotin and its Triphenylphosphine Complex 31 2.10 Silicon Oxygen Compounds and Siloxane Polymers 33 2.11 Preparation and NMR Identification of Two Phosphorus Esters 36 2.12 The Preparation of Potassium Peroxodisulfate, K2S208 38 2.13 K2ON(S03)2 (Fremy's Salt) and [Ph3PCH2C6H4CH2PPh3]ON(S03)2 41 2.14 Polyiodides, Me4NIx 43 2.15 Interhalogen Compounds 45 2.16 Simulation of Atomic and Molecular Orbitals 50

3 Intermediate Experiments 57

3.1 Ferrocene, (/y5-C5H5)2Fe, and Its Derivatives 59 3.2 The Use of Organolithium Reagents in the Preparation of Ferrocene Derivatives 61 3.3 Complexes of л-Bonding Arene Ligands 67 3.4 Organotin Chemistry 69 3.5 Nickel Catalysed Cross-Coupling of Alkylmagnesium with Haloarene 76 3.6 Transition Metal Catalysis 80 3.7 Transition Metal-Carbon Bonds in Chemistry and Biology 83 3.8 Cobalt Complexes of Dioxygen 94 3.9 Preparation of Nitrosyl Complexes of Iron and Nickel 96 3.10 Preparation of an Iron Dinitrogen Complex 99 3.11 Nickel Dihalide Phosphine Complexes 101 3.12 Influence of Ligand Field Tetragonahty on the Ground-State Spin of Nickel(n)

Complexes 104 3.13 Preparation of trans-PtUCl(PPh3)2 and Its 'H, 31P and 195Pt NMR Spectra.. 107 3.14 Identification of Stereochemical (Geometrical) Isomers of Mo(CO)4L2 by

Infra-Red Spectroscopy 110 3.15 Five Coordinate Complexes: [VO(acac)2] and [Cr(NH3)6][CuCl5] 113 3.16 Metal Acetylacetonate Complexes: Preparation and Characterisation 116

X Contents

3.18 The Synthesis and Coordination Chemistry of Macrocyclic Complexes 133 3.19 Synthesis and Reactivity of Tertiary Phosphines 138 3.20 Inorganic Heterocycles: Cyclophosphazenes 142 3.21 Inorganic (Carbon-Free) Chelate Rings: A Dithioimidophosphinato Ligand and

Some of its Metal Complexes 145 3.22 Amidosulphuric Acid, Trisilveramidosulphate-Monohydrate and S03 • N(CH3)3

Complexes 150 3.23 Four Methods for Analysing First Order Kinetics 154 3.24 Symmetries of Inorganic Molecules and Applications of Group Theory and

Graph Theory 160

4 Advanced Experiments 185

4.1 Chloro?ra(tert-butylimido)manganese(vn) 187 4.2 2,2': 6',2"-Terpyridine Complexes and Metal Directed Reactivity 189 4.3 Electronic Characterisation of a Transition-Metal Complex Using Electroche­

mical, UV/Vis and EPR Techniques 191 4.4 The Synthesis of n6-Arenetricarbonyl Chromium(O) Complexes 194 4.5 Migratory Insertion Reactions in Organo Transition-Metal Chemistry 197 4.6 Organometallic Molybdenum Complexes 202 4.7 The Preparation of rac-Ethylene-l,2-bis(l-indenyl)zirconium Dichloride and

Dibenzyl Complexes 207 4.8 Halfsandwich Carbonyl Vanadium Complexes 211 4.9 Covalent and Ionic Metallocene Hexafluoroarsenate Complexes 217 4.10 Preparation of the Iron Tricarbonyl Complex of Methyl-2-acetamidoacrylate . 220 4.11 A Transition-Metal Alkylidyne Complex 222 4.12 Preparation of [Bu4N][B3H8] and the Formation of RuH(B3H8)(CO)(PPh3)2 . 225 4.13 Vacuum Line Techniques: Preparation of SiF4 and SiF4(C5H5N)2 228 4.14 Preparation and Structure of the Acetyl Chloride-Antimony Pentachloride

Complex 232 4.15 Arsenium Cations: Carbene Analogues 235 4.16 Preparation and Some Reactions of the Folded P2N4S2 Ring 239 4.17 Sulphur Rich Homocycles and Heterocycles: Titanocene Pentasulphide, Cyclo-

Heptasulphur and 1,2,3,4,5,6,7-Heptathionane 243 4.18 Reactions of Alkali Metal Polyselenides and Polytellurides with Group 6 Metal

Carbonyls 246 4.19 Sulphur-Nitrogen Heterocycles and [SN04]j. Polymer 250 4.20 Chlorothionitrene and Cyc/othiazeno Complexes of Tungsten 254 4.21 Selenium-Nitrogen and Tellurium-Nitrogen Compounds 257 4.22 Low Temperature Synthesis of Barium Amides and Phenoxides 260 4.23 Structural, Electrical and Magnetic Properties of Perovskite Ceramics 265 4.24 Metal-containing Liquid Crystals. The Synthesis of Trans-bis, (4-alkyl-4'-cyano-

l,l'-biphenyl)-dichloroplatinum(n) and Related Species - The Use of Melt Syntheses 271

4.25 Magnetochemistry Experiments: Exchange Coupling in Copper(n)-Nickel(n) Bimetallic Complexes and Spin Transition in Iron Complexes 279

Index 283