THE BOYS' PLAYBOOK OF CHEMISTRY

By PAUL SANCHEZ

CONTENTS THE CENTRAL ATOM KEY CONCEPTS IN COORDINATION CHEMISTRY A WHO’S WHO OF METAL IONS COMMONERS AND ‘UNCOMMONERS’ REDE?NING COMMONERS METALS IN MOLECULES METALS IN THE NATURAL WORLD METALS IN CONTRIVED ENVIRONMENTS NATURAL OR MADE-TO-MEASURE COMPLEXES THE ROAD AHEAD CONCEPT KEYS FURTHER READING LIGANDS MEMBERSHIP: BEING A LIGAND WHAT MAKES A LIGAND? MAKING ATTACHMENTS – COORDINATION PUTTING THE BITE ON METALS – CHELATION DO I LOOK BIG ON THAT? – CHELATE RING SIZE DIFFERENT TRIBES – DONOR GROUP VARIATION LIGANDS WITH MORE BITE – DENTICITY MONODENTATE LIGANDS – THE SIMPLE TYPE BASIC BINDERS AMINES AIN’T AMMINES – LIGAND FAMILIES MEETING MORE METALS – BRIDGING LIGANDS GREED IS GOOD – POLYDENTATE LIGANDS THE SIMPLE CHELATE MORE TEETH, STRONGER BITE – POLYDENTATES MANY-ARMED MONSTERS – INTRODUCING LIGAND SHAPE POLYNUCLEATING SPECIES – MOLECULAR BIGAMISTS WHEN ONE IS NOT ENOUGH VIVE LA DIFFERENCE – MIXED-METAL COMPLEXATION SUPERSIZED – BINDING TO MACROMOLECULES A SEPARATE RACE – ORGANOMETALLIC SPECIES COMPLEXES THE CENTRAL METAL ION METAL–LIGAND MARRIAGE THE COORDINATE BOND THE FOUNDATION OF COORDINATION CHEMISTRY COMPLEX SHAPE – NOT JUST ANY WHICH WAY HOLDING ON – THE NATURE OF BONDING IN METAL COMPLEXES AN IONIC BONDING MODEL – INTRODUCING CRYSTAL FIELD THEORY A COVALENT BONDING MODEL – EMBRACING MOLECULAR ORBITAL THEORY LIGAND FIELD THEORY – MAKING COMPROMISES BONDING MODELS EXTENDED COUPLING – POLYMETALLIC COMPLEXES MAKING CHOICES SELECTIVITY – OF ALL THE MOLECULES IN ALL THE WORLD, WHY THIS ONE? PREFERENCES – DO YOU LIKE WHAT I LIKE? COMPLEX LIFETIMES – TOGETHER, FOREVER? COMPLEXATION CONSEQUENCES SHAPE GETTING IN SHAPE FORMS OF COMPLEX LIFE – COORDINATION NUMBER AND SHAPE ONE COORDINATION (ML) TWO COORDINATION (ML2) THREE COORDINATION (ML3) FOUR COORDINATION (ML4) FIVE COORDINATION (ML5) SIX COORDINATION (ML6) HIGHER COORDINATION NUMBERS (ML7 TO ML9) IN?UENCING SHAPE METALLIC GENETICS – METAL ION IN?UENCES MOULDING A RELATIONSHIP – LIGAND IN?UENCES CHAMELEON COMPLEXES ISOMERISM – REAL 3D EFFECTS INTRODUCING STEREOISOMERS CONSTITUTIONAL (STRUCTURAL) ISOMERISM STEREOISOMERISM: IN PLACE – POSITIONAL ISOMERS; IN SPACE – OPTICAL ISOMERS WHAT’S BEST? – ISOMER PREFERENCES SOPHISTICATED SHAPES COMPOUNDS OF POLYDENTATE LIGANDS ENCAPSULATION COMPOUNDS HOST–GUEST MOLECULAR ASSEMBLIES DE?NING SHAPE STABILITY THE MAKINGS OF A STABLE RELATIONSHIP BEDDED DOWN – THERMODYNAMIC STABILITY FACTORS IN?UENCING STABILITY OF METAL COMPLEXES OVERALL STABILITY CONSTANTS UNDERGOING CHANGE – KINETIC STABILITY COMPLEXATION – WILL IT LAST? THERMODYNAMIC AND KINETIC STABILITY KINETIC RATE CONSTANTS LABILITY AND INERTNESS IN OCTAHEDRAL COMPLEXES REACTIONS A NEW PARTNER – SUBSTITUTION A NEW BODY – STEREOCHEMICAL CHANGE A NEW FACE – OXIDATION–REDUCTION A NEW SUIT – LIGAND-CENTRED REACTIONS SYNTHESIS MOLECULAR CREATION – WAYS TO MAKE COMPLEXES CORE METAL CHEMISTRY – PERIODIC TABLE IN?UENCES S BLOCK: ALKALI AND ALKALINE EARTH METALS P BLOCK: MAIN GROUP METALS D BLOCK: TRANSITION METALS F BLOCK: INNER TRANSITION METALS (LANTHANOIDS AND ACTINOIDS) BEYOND NATURAL ELEMENTS REACTIONS INVOLVING THE COORDINATION SHELL LIGAND SUBSTITUTION REACTIONS IN AQUEOUS SOLUTION SUBSTITUTION REACTIONS IN NONAQUEOUS SOLVENTS SUBSTITUTION REACTIONS WITHOUT USING A SOLVENT CHIRAL COMPLEXES CATALYSED REACTIONS REACTIONS INVOLVING THE METAL OXIDATION STATE REACTIONS INVOLVING COORDINATED LIGANDS METAL-DIRECTED REACTIONS REACTIONS OF COORDINATED LIGANDS ORGANOMETALLIC SYNTHESIS PROPERTIES FINDING WAYS TO MAKE COMPLEXES TALK – INVESTIGATIVE METHODS GETTING PHYSICAL – METHODS AND OUTCOMES PROBING THE LIFE OF COMPLEXES – USING PHYSICAL METHODS PEAK PERFORMANCE – ILLUSTRATING SELECTED PHYSICAL METHODS PRETTY IN RED? – COLOUR AND THE SPECTROCHEMICAL SERIES A MAGNETIC PERSONALITY? – PARAMAGNETISM AND DIAMAGNETISM LIGAND FIELD STABILIZATION A COMPLEX LIFE LIFE’S A METAL ION BIOLOGICAL LIGANDS METAL IONS IN BIOLOGY CLASSES OF METALLOBIOMOLECULES METALLOPROTEINS AND METALLOENZYMES IRON-CONTAINING BIOMOLECULES COPPER-CONTAINING BIOMOLECULES ZINC-CONTAINING BIOMOLECULES OTHER METAL-CONTAINING BIOMOLECULES MIXED-METAL PROTEINS DOING WHAT COMES UNNATURALLY – SYNTHETIC BIOMOLECULES A LABORATORY-FREE APPROACH – IN SILICO PREDICTION COMPLEXES AND COMMERCE KILL OR CURE? – COMPLEXES AS DRUGS INTRODUCING METALLODRUGS ANTICANCER DRUGS OTHER METALLODRUGS HOW MUCH? – ANALYSING WITH COMPLEXES FLUOROIMMUNOASSAY FLUOROIONOPHORES PRO?TING FROM COMPLEXATION METAL EXTRACTION INDUSTRIAL ROLES FOR LIGANDS AND COORDINATION COMPLEXES BEING GREEN COMPLEXATION IN REMEDIATION BETTER WAYS TO SYNTHESIZE FINE ORGANIC CHEMICALS COMPLEX FUTURES TAKING STOCK CRYSTAL BALL GAZING