Mass Spectrometry of Inorganic and Organometallic Compounds

William Henderson is the author of Mass Spectrometry of Inorganic and Organometallic Compounds: Tools - Techniques - Tips, published by Wiley.J. Scott McIndoe is the author of Mass Spectrometry of Inorganic and Organometallic Compounds: Tools - Techniques - Tips, published by Wiley.

"Although this book has been specifically written for inorganic and organometallic chemistry, researchers working in other fields can also learn not only about the basic principles and techniques of mass-spectrometry but also can learn of its applications." (The Higher Education Academy Physical Sciences Centre, June 2008)"Valuable addition to those already written covering mass spectrometry." (Reviews, June 2008)

• Preface xvList of commonly-used abbreviations xix1 Fundamentals 11.1 Introduction 11.2 Inlets 11.3 Collision-Induced Dissociation 21.3.1 Bond dissociation energies from CID studies 41.3.2 Presentation of CID data 41.4 Detectors 61.5 Mass Resolution 71.5.1 Mass accuracy 101.6 Data Processing 121.7 Isotopes 141.7.1 Isotopic abundances of the elements 171.7.2 Isotope pattern matching 19References 212 Mass analysers 232.1 Introduction 232.2 Sectors 232.2.1 Ms/ms 262.2.2 Summary 262.3 Quadrupoles 272.3.1 Ms/ms 292.3.2 Summary 302.4 Quadrupole Ion Trap 302.4.1 MS/MS and MS n 332.4.2 Summary 342.5 Time-of-Flight 352.5.1 Reflectron instruments 372.5.2 Orthogonal TOF (oa-TOF) 382.5.3 Ms/ms 382.5.4 Summary 402.6 Fourier Transform Ion Cyclotron Resonance 402.6.1 Ms/ms 432.6.2 Summary 44References 453 Ionisation techniques 473.1 Introduction 473.2 Electron Ionisation 473.2.1 Fragmentation of metal-containing compounds 503.2.2 Applications 513.2.3 Summary 533.3 Chemical Ionisation 543.3.1 Applications 563.3.2 Summary 573.4 Field Ionisation/Field Desorption 583.4.1 Summary 593.5 Plasma Desorption 603.5.1 Applications 603.5.2 Summary 623.6 Fast Atom Bombardment / Liquid Secondary Ion Mass Spectrometry 623.6.1 Matrices 633.6.2 Ions observed in FAB/LSIMS 653.6.3 Applications 663.6.4 Summary 713.7 Matrix Assisted Laser Desorption Ionisation 723.7.1 Matrices 753.7.2 MALDI of air-sensitive samples 763.7.3 Applications 773.7.4 Summary 873.8 Inductively Coupled Plasma Mass Spectrometry 883.8.1 Applications 893.8.2 Summary 903.9 Electrospray Ionisation 903.9.1 Electrochemistry in the ESI process 923.9.2 Multiply-charged species 943.9.3 Nanospray 953.9.4 ESI MS: Practical considerations 963.9.5 Applications 993.9.6 Summary 99References 1004 The ESI MS behaviour of simple inorganic compounds 1074.1 Introduction 1074.2 Simple Metal Salts 1074.2.1 Salts of Singly-charged Ions, M+ X-1074.2.2 Salts of multiply-charged ions, e.g M2+(X-)2 ,M3+ (X)3 etc 1124.2.3 Negative-ion ESI mass spectra of metal salts 1164.2.4 ESI MS behaviour of easily-reduced metal ions: copper(II), iron(III) and mercury(II) 1174.3 Polyanions Formed by Main Group Elements 1194.4 Oxoanions Formed by Main Group Elements 1194.5 Borane Anions 1224.6 Fullerenes 1224.7 Inorganic Phosphorus Compounds: Phosphoranes and Cyclophosphazenes 1234.8 Summary 123References 1235 The ESI MS behaviour of coordination complexes 1275.1 Introduction 1275.2 Charged, ‘Simple’ Coordination Complexes 1285.2.1 Cationic coordination complexes 1285.2.2 Anionic metal halide complexes 1325.2.3 Highly-charged, anionic transition metal complexes – cyanometallate anions. 1345.3 (Neutral) Metal Halide Coordination Complexes 1365.4 Metal Complexes of Polydentate Oxygen Donor Ligands: Polyethers, Crown Ethers, Cryptands and Calixarenes 1395.5 Porphyrins and Metalloporphyrins 1415.6 Metal Alkoxides – Highly Moisture-Sensitive Coordination Compounds 1445.7 β-Diketonate Complexes 1455.8 Metal Complexes of Carbohydrates 1485.9 Metal Complexes of Amino Acids, Peptides and Proteins 1495.9.1 Amino acids 1495.9.2 Proteins and peptides 1505.10 Oxoanions, Polyoxoanions and Related Species 1515.10.1 Simple transition metal oxoanions 1515.10.2 Reactivity studies involving molybdate and tungstate ions 1545.10.3 Polyoxoanions 1555.10.4 Miscellaneous oxo complexes 1575.11 Metal Clusters 1575.12 Compounds with Anionic Sulfur and Selenium Donor Ligands 1585.12.1 Metal sulfide, selenide and related complexes 1585.12.2 Metal dithiocarbamate and dithiophosphate complexes 1595.12.3 Metal thiolate complexes 1605.13 Characterisation of Metal-Based Anticancer Drugs, their Reaction Products and Metabolites 1635.13.1 Characterisation of anticancer-active platinum complexes 1635.13.2 Reactions of platinum anticancer drugs with biomolecules and detection of metabolites 1655.13.3 Other non-platinum anticancer agents 1665.14 In situ Formation of Coordination Complexes as an Ionisation Technique 1665.15 Summary 167References 1686 The ESI MS behaviour of main group organometallic compounds 1756.1 Introduction 1756.2 Organometallic Derivatives of Group 14 Elements 1756.2.1 Organosilicon compounds 1756.2.2 Organogermanium compounds 1766.2.3 Organotin compounds 1766.2.4 Organolead compounds 1786.3 Organometallic Derivatives of Group 15 Elements 1806.3.1 Organophosphorus compounds 1806.3.2 Organoarsenic compounds 1856.3.3 Organoantimony and -bismuth compounds 1876.4 Organometallic Derivatives of Group 16 Elements; Organosulfur, -Selenium and -Tellurium Compounds 1886.5 Organomercury Compounds 1886.6 Other Organometallic Derivatives 1906.7 Summary 190References 1907 The ESI MS behaviour of transition metal and lanthanide organometallic compounds 1957.1 Introduction 1957.2 Metal Carbonyl Complexes 1957.2.1 Ionic mononuclear metal carbonyl compounds 1967.2.2 Ionic metal carbonyl clusters 1967.2.3 Neutral metal carbonyl compounds 1987.2.4 Oxidation and reduction processes involving metal carbonyls 2017.2.5 Characterisation of reaction mixtures involving metal carbonyl clusters 2017.2.6 Fragmentation of transition metal carbonyl clusters; electrospray as a source of bare metal clusters 2037.2.7 The use of ‘Electrospray-friendly’ ligands in organometallic chemistry 2047.3 Metal Isocyanide Complexes 2047.4 Metal Cyclopentadienyl and Related Complexes 2057.4.1 Ferrocene-based compounds 2057.4.2 Use of ferrocene derivatives as electroactive derivatisation agents for electrospray ionisation 2097.4.3 Other metallocene systems 2107.4.4 Monocyclopentadienyl complexes 2107.5 η3 Metal 3 -allyl Complexes 2117.6 Metal Arene Complexes 2127.7 Formation of π-Hydrocarbon Complexes and their Use as an Ionisation Aid 2127.8 Metal-Acetylene/acetylide Complexes and Complexes of Metal-Acetylides 2137.9 Transition Metal -Alkyl and Aryl Complexes 2147.10 Mass Spectrometry of Lanthanide Organometallic Complexes 2157.11 Summary 215References 2158 A selection of special topics 2218.1 Introduction 2218.2 Characterisation of Dendrimers Using ESI and MALDI-TOF MS Techniques 2218.3 Investigating the Formation of Supramolecular Coordination Assemblies Using ESI MS 2228.4 Using ESI MS as a Tool for Directing Chemical Synthesis: A Case Study Involving the Platinum Metalloligands [Pt 2 (µ–E) 2 (PPh 3) 4] 2248.4.1 Background 2248.4.2 Analysis of the metalloligands; formation of protonated species 2258.4.3 Reactivity of [Pt 2 (µ–E) 2 (PPh 3) 4] towards metal-halide complexes 2268.5 Applications of ESI MS in the Detection of Reactive Intermediates and Catalyst Screening 2288.5.1 Detection of intermediates in reactions of organic compounds 2288.5.2 Detection and chemistry of reaction intermediates in the gas phase 2308.5.3 Screening of new catalysts using mass spectrometry 231References 232Appendix 1 Naturally occurring isotopes 235Appendix 2 Periodic table of the elements 247Appendix 3 Alphabetical list of elements 249Appendix 4 Glossary of terms 251Appendix 5 Useful sources of information 265Index 267