Chemistry of theElementsSecond Edition
N . N . GREENWOOD and A. EARNSHAWSchool of ChemistryUniversity of Leeds, U.K.
AMSTERDAM " BOSTON " HEIDELBERG " LONDON
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Contents
Preface to the second editionPreface to the first edition
Chapter 1
Origin of the Elements . Isotopes and Atomic Weights
11 .1 Introduction1 .2
Origin of the Universe1 .3
Abundances of the Elements in the Universe1 .4
Stellar Evolution and the Spectral Classes of Stars1 .5
Synthesis of the Elements1 .5 .1
Hydrogen burning1 .5 .2
Helium burning and carbon burning1 .5 .3
The a-process1 .5 .4
The e-process (equilibrium process)1 .5 .5
The s- and r-processes (slow and rapid neutron absorption)1 .5 .6
The p-process (proton capture)1 .5 .7
The x-process1 .6
Atomic Weights1 .6 .1
Uncertainty in atomic weights1 .6 .2
The problem of radioactive elements
Chapter 2
Chemical Periodicity and the Periodic Table2 .1 Introduction2.2
The Electronic Structure of Atoms2.3
Periodic Trends in Properties2 .3 .1
Trends in atomic and physical properties2 .3 .2
Trends in chemical properties2.4
Prediction of New Elements and Compounds
Chapter 3
Hydrogen
323 .1 Introduction3.2
Atomic and Physical Properties of Hydrogen3.2 .1
Isotopes of hydrogen3.2 .2
Ortho- and para-hydrogen3.2 .3
Ionized forms of hydrogen3.3
Preparation, Production and Uses3.3.1 Hydrogen3.3.2 Deuterium3 .3 .3 Tritium
3.4
Chemical Properties and Trends3AI
The coordination chemistry of hydrogen
v
I13599101112121313151618
20202123232729
3234343536383839414344
3 .5
Protonic Acids and Bases3 .6
The Hydrogen Bond3.6 .1
Influence on properties3 .6 .2
Influence on structure3 .6 .3
Strength of hydrogen bonds and theoretical description3 .7
Hydrides of the Elements
485253596164
Chapter 4
Lithium, Sodium, Potassium, Rubidium, Caesium and
68Francium4 .1 Introduction
684.2
The Elements
684.2 .1
Discovery and isolation
684.2.2
Terrestrial abundance and distribution
694.2.3
Production and uses of the metals
714.2.4
Properties of the alkali metals
744.2.5
Chemical reactivity and trends
764.2.6
Solutions in liquid ammonia and other solvents
774.3 Compounds
794.3.1
Introduction : the ionic-bond model
794.3.2
halides and hydrides
824,3.3
Oxides, peroxides, superoxides and suboxides
844.3.4 Hydroxides
864.3.5
Oxoacid salts and other compounds
874.3.6
Coordination chemistry
904.3.7 . Imides, amides and related compounds
994.3.8
Organometallic compounds
102
Chapter 5
Beryllium, Magnesium, Calcium, Strontium, Barium and
107Radium5 .1 Introduction
1075.2
The Elements
1085.2 .1
Terrestrial abundance and distribution
1085.2 .2
Production and uses of the metals
1105.2 .3
Properties of the elements
1115.2 .4
Chemical reactivity and trends
1125.3 Compounds
1135.3 .1 Introduction
1135.3 .2
Hydrides and halides
1155.3 .3
Oxides and hydroxides
1195.3 .4
Oxoacid salts and coordination complexes
1225.3 .5
Organometallic compounds
127Beryllium
127Magnesium
131Calcium, strontium and barium
136
Chapter 6
Boron
1396.1 Introduction
1396.2 Boron
1406.2 .1
Isolation and purification of the element
1406.2.2
Structure of crystalline boron
1416.2 .3
Atomic and physical properties of boron
1446.2.4
Chemical properties
1446.3 Borides
1456.3.1 Introduction
1456.3.2
Preparation and stoichiometry
1466.3 .3
Structures of borides
147
Contents
vii
6.4
Bpranes (Boron Hydrides)
1516.4 .1 Introduction
1516.4.2
Bonding and topology
1576.4.3
Preparation and properties of boranes
1626.4.4
The chemistry of small boranes and their anions (Bt -B4)
1646.4.5
Intermediate-sized boranes and their anions (B5-B9)
1706.4.6
Chemistry of nido-decaborane, BlOH14
1736.4.7
Chemistry of closo-B� H� 2-
1786.5 Carboranes
1816.6 Metallocarboranes
1896.7
Boron Halides
1956.7 .1
Boron trihalides
1956.7 .2
Lower halides of boron
2006.8
Boron-Oxygen Compounds
2036.8 .1
Boron oxides and oxoacids
2036.8.2 Borates
2056.8 .3
Organic compounds containing boron-oxygen bonds
2076.9
Boron-Nitrogen Compounds
2076.10
Other Compounds of Boron
2116.10.1
Compounds with bonds to P, As or Sb
2116.10.2
Compounds with bonds to S, Se and Te
213
Chapter 7
Aluminium, Gallium, Indium and Thallium
2167 .1 Introduction
2167.2
The Elements
2177.2 .1
Terrestrial abundance and distribution
2177.2.2
Preparation and uses of the metals
2197.2.3
Properties of the elements
2227.2 .4
Chemical reactivity and trends
2247.3 Compounds
2277.3 .1
Hydrides and related complexes
2277.3 .2
Halides and halide complexes
233Aluminium trihalides
233Tribalides of gallium, indium and thallium
237Lower halides of gallium, indium and thallium
2407.3 .3
Oxides and hydroxides
2427.3 .4
Ternary and more complex oxide phases
247Spinels and related compounds
247Sodium-ß-alumina and related phases
249Tricalcium aluminate, Ca3A1206
2517.3 .5
Other inorganic compounds
252Chalcogenides
252Compounds with bonds to N, P, As, Sb or Bi
255Some unusual stereochemistries
2567.3.6
Organometallic compounds
257Organoaluminium compounds
258Organometallic compounds of Ga, In and TI
262Al-N heterocycles and clusters
265
Chapter 8
Carbon
2688 .1 Introduction
2688.2 Carbon
2698.2.1
Terrestrial abundance and distribution
2698.2.2
Allotropic forms
2748.2.3
Atomic and physical properties
2768.2.4 Fullerenes
278Structure of the fullerenes
280Other molecular allotropes of carbon
282Chemistry of the fullerenes
282Reduction of fullerenes to fullerides
285
Viii
Contents
Chapter 9
Silicon
328
Chapter 10
Germanium, Tin and Lead
367
Chapter 11
Nitrogen
Addition reactions
286Heteroatom fullerene-type clusters
287Encapsulation of metal atoms by fullerene clusters
2888.2 .5
Chemical properties of carbon
2898.3
Graphite Intercalation Compounds
2938.4 Carbides
296Metallocarbohedrenes (met-cars)
3008.5
Hydrides, Halides and Oxohalides
3018.6
Oxides and Carbonates
3058.7
Chalcogenides and Related Compounds
3138.8
Cyanides and Other Carbon-Nitrogen Compounds
3198.9
Organometallic Compounds
326
9.1 Introduction
3289.2 Silicon
3299.2 .1
Occurrence and distribution
3299.2.2
Isolation, production and industrial uses
3309.2 .3
Atomic and physical properties
3309.2.4
Chemical properties
3319.3 Compounds
3359.3 .1 Silicides
3359.3.2
Silicon hydrides (silanes)
3379.3 .3
Silicon halides and related complexes
3409.3.4
Silica and silicic acids
3429.3 .5
Silicate minerals
347Silicates with discrete units
347Silicates with chain or ribbon structures
349Silicates with layer structures
349Silicates with framework structures
3549.3.6
Other inorganic compounds of silicon
3599.3 .7
Organosilicon compounds and silicones
361
10.1 Introduction
36710.2
The Elements
36810.2.1
Terrestrial abundance and distribution
36810.2.2
Production and uses of the elements
36910.2.3
Properties of the elements
37110.2.4
Chemical reactivity and group trends
37310.3 Compounds
37410.3 .1
Hydrides and hydrohalides
37410.3 .2
Halides and related complexes
375Germanium halides
376Tin halides
377Lead halides
38110.3 .3
Oxides and hydroxides
38210.3 .4
Derivatives of oxoacids
38710.3 .5
Other inorganic compounds
38910.3 .6
Metal-metal bonds and clusters
39110.3.7
Organometallic compounds
396Germanium
396Tin
399Lead
404
11.1 Introduction406406
11 .2
The Element
40711 .2 .1
Abundance and distribution
40711 .2 .2
Production and uses of nitrogen
40911 .2 .3
Atomic and physical properties
41111 .2 .4
Chemical reactivity
41211 .3 Compounds
41611 .3 .1
Nitrides, azides and nitrido complexes
41711 .3 .2
Ammonia and ammonium salts
420Liquid ammonia as a solvent
42411 .3 .3
Other hydrides of nitrogen
426Hydrazine
427Hydroxylamine
431Hydrogen azide
43211 .3 .4
Thermodynamic relations between N-containing species
43411 .3 .5
Nitrogen halides and related compounds
43811 .3 .6
Oxides of nitrogen
443Nitrous oxide, N20
443Nitric oxide, NO
445Dinitrogen trioxide, N203
454Nitrogen dioxide, N02, and dinitrogen tetroxide, N204
455Dinitrogen pentoxide, N205, and nitrogen trioxide, N03
45811 .3 .7
Oxoacids, oxoanions and oxoacid salts of nitrogen
459Hyponitrous acid and hyponitrites
459Nitrous acid and nitrites
461Nitric acid and nitrates
465Orthonitrates, M3N04
471
Chapter 12
Phosphorus
473
12 .1 Introduction
47312.2
The Element
47512.2 .1
Abundance and distribution
47512.2.2
Production and uses of elemental phosphorus
47912.2 .3
Allotropes of phosphorus
47912.2.4
Atomic and physical properties
48212.2 .5
Chemical reactivity and stereochemistry
48312.3 Compounds
48912.3 .1 Phosphides
48912.3 .2
Phosphine and related compounds
49212.3 .3
Phosphorus halides
495Phosphorus trihalides
495Diphosphorus tetrahalides and other lower halides of phosphorus
497Phosphorus pentahalides
498Pseudohalides of phosphorus(III)
50112.3 .4
Oxohalides and thiohalides of phosphorus
50112.3 .5
Phosphorus oxides, sulfides, selenides and related compounds
503Oxides
503Sulfides
506Oxosulfides
51012.3 .6
Oxoacids of phosphorus and their salts
510Hypophosphorous acid and hypophosphites [H2PO(OH) and H2PO2-J
513Phosphorous acid and phosphites [HPO(OH)2 and HP032- ]
514Hypophosphoric acid (H4P206) and hypophosphates
515Other lower oxoacids of phosphorus
516The phosphoric acids
516Orthophosphates
523Chain polyphosphates
526Cyclo-polyphosphoric acids and cyclo-polyphosphates
52912.3 .7
Phosphorus-nitrogen compounds
531Cyclophosphazanes
533Phosphazenes
534
PolyphosphazenesApplications
12 .3 .8
Organophosphorus compounds
Chapter 13
Arsenic, Antimony and Bismuth
547
13 .1 Introduction
54713 .2
The Elements
54813.2.1
Abundance, distribution and extraction
54813 .2.2
Atomic and physical properties
55013 .2 .3
Chemical reactivity and group trends
55213 .3
Compounds of Arsenic, Antimony and Bismuth
55413 .3 .1
Intermetallic compounds and alloys
55413 .3 .2
Hydrides of arsenic, antimony and bismuth
55713 .3 .3
Halides and related complexes
558Trihalides, MX3
558Pentahalides, MXS
561Mixed halides and lower halides
563Halide complexes of M111 and Mv
564Oxide halides
57013.3 .4
Oxides and oxo compounds
572Oxo compounds of MIII
573Mixed-valence oxides
576Oxo compounds of MV576
13.3.5
Sulfides and related compounds
57813.3 .6
Metal-metal bonds and clusters
58313.3 .7
Other inorganic compounds
59113.3 .8
Organometallic compounds
592Organoarsenic(III) compounds
593Organoarsenic(V) compounds
594Physiological activity of arsenicals
596Organoantimony and organobismuth compounds
596
Chapter 14
Oxygen
60014 .1
The Element14 .1 .1 Introduction14 .1 .2 Occurrence14 .1 .3 Preparation14 .1 .4
Atomic and physical properties14 .1 .5
Other forms of oxygenOzoneAtomic oxygen
14.1 .6
Chemical properties of dioxygen, OZ14.2
Compounds of Oxygen14.2 .1
Coordination chemistry : dioxygen as a ligand14.2 .2 Water
IntroductionDistribution and availabilityPhysical properties and structureWater of crystallization, aquo complexes and solid hydratesChemical propertiesPolywater
14 .2.3
Hydrogen peroxidePhysical propertiesChemical properties
14 .2 .4
Oxygen fluorides14 .2.5 Oxides
Various methods of classificationNonstoichiometry
536542542
600600602603604607607611612615615620620621623625627632633633634638640640642
Chapter 15
Sulfur
64515 .1
The Element
64515.1 .1 Introduction
64515.1 .2
Abundance and distribution
64715.1 .3
Production and uses of elemental sulfur
64915.1 .4
Allotropes of sulfur
65215.1 .5
Atomic and physical properties
66115.1 .6
Chemical reactivity
662Polyatomic sulfur cations
664Sulfur as a ligand
665Other ligands containing sulfur as donor atom
67315.2
Compounds of Sulfur
67615.2 .1
Sulfides of the metallic elements
676General considerations
676Structural chemistry of metal sulfides
679Anionic polysulfides
68115.2 .2
Hydrides of sulfur (sulfanes)
68215.2 .3
Halides of sulfur
683Sulfur fluorides
683Chlorides, bromides and iodides of sulfur
68915.2 .4
Oxohalides of sulfur
69315.2 .5
Oxides of sulfur
695Lower oxides
695Sulfur dioxide, S02
698Sulfur dioxide as a ligand
701Sulfur trioxide
703Higher oxides
70415.2 .6
Oxoacids of sulfur
706Sulfuric acid, H2SO4
710Peroxosulfuric acids, H2SO5 and H2S208
712Thiosulfuric acid, H2S203
714Dithionic acid, H2S206
715Polythionic acids, H2S"O6
716Sulfurous acid, H2SO3
717Disulfurous acid, H2S205
720Dithionous acid, H2S204
72015.2 .7
Sulfur-nitrogen compounds
721Binary sulfur nitrides
722Sulfur-nitrogen cations and anions
730Sulfur imides, S8- �(NH) �
735Other cyclic sulfur-nitrogen compounds
736Sulfur-nitrogen-halogen compounds
736Sulfur-nitrogen-oxygen compounds
Chapter 16
Selenium, Tellurium and Polonium 74716 .1
The Elements
74716.1 .1
Introduction: history, abundance, distribution
74716.1 .2
Production and uses of the elements
74816.1 .3 Allotropy
75116.1 .4
Atomic and physical properties
75316.1 .5
Chemical reactivity and trends
75416.1 .6
Polyatomic cations, M,r"}
75916.1 .7
Polyatomic anions, Mx2-
76216.2
Compounds of Selenium, Tellurium and Polonium
76516.2 .1
Selenides, tellurides and polonides
76516.2.2 Hydrides
76616.2 .3 Halides
767Lower halides
768Tetrahalides
772
xii
Contents
HexahalidesHalide complexes
16 .2 .4
Oxohalides and pseudohalides16 .2 .5 Oxides16 .2 .6
Hydroxides and oxoacids16 .2 .7
Other inorganic compounds16 .2 .8 Organo-compounds
775776777779781783786
Chapter 17
The Halogens: Fluorine, Chlorine, Bromine, Iodine and
789Astatine
17 .1
The Elements
78917 .1 .1 Introduction
789Fluorine
789Chlorine
792Bromine
793Iodine
794Astatine
79417 .1 .2
Abundance and distribution
79517 .1 .3
Production and uses of the elements
79617 .1 .4
Atomic and physical properties
80017 .1 .5
Chemical reactivity and trends
804General reactivity and stereochemistry
804Solutions and charge-transfer complexes
80617.2
Compounds of Fluorine, Chlorine, Bromine and Iodine
80917 .2 .1
Hydrogen halides, HX
809Preparation and uses
809Physical properties of the hydrogen halides
812Chemical reactivity of the hydrogen halides
813The hydrogen halides as nonaqueous solvents
81617 .2 .2
Halides of the elements
819Fluorides
820Chlorides, bromides and iodides
82117.2 .3
Interhalogen compounds
824Diatomic interhalogens, XY
824Tetra-atomic interhalogens, XY3
828Hexa-atomic and octa-atomic interhalogens, XFS and IFS
83217.2.4
Polyhalide anions
83517.2.5
Polyhalonium cations XYZ� +
83917.2.6
Halogen cations
84217.2 .7
Oxides of chlorine, bromine and iodine
844Oxides of chlorine
844Oxides of bromine
850Oxides of iodine
85117.2 .8
Oxoacids and oxoacid salts
853General considerations
853Hypohalous acids, HOX, and hypohalites, XO-
856Halous acids, HOXO, and halites, XOZ-
859Halic acids, HOXOZ, and halates, X03-
862Perhalic acid and perhalates
865Perchloric acid and perchlorates
865Perbromic acid and perbromates
871Periodic acids and periodates
87217.2.9
Halogen oxide fluorides and related compounds
875Chlorine oxide fluorides
875Bromine oxide fluorides
880Iodine oxide fluorides
88117.2.10 Halogen derivatives of oxoacids
88317.3
The Chemistry of Astatine885
Contents
xiii
Chapter 18
The Noble Gases: Helium, Neon, Argon, Krypton, Xenon
888and Radon18 .1 Introduction18 .2
The Elements18 .2 .1
Distribution, production and uses18 .2 .2
Atomic and physical properties of the elements18 .3
Chemistry of the Noble Gases18 .3 .1 Clathrates18 .3 .2
Compounds of xenon18 .3 .3
Compounds of other noble gases
888889889890892893893903
Chapter 19
Coordination and Organometallic Compounds
90519.1 Introduction
90519.2
Types of Ligand
90619.3
Stability of Coordination Compounds
90819.4
The Various Coordination Numbers
91219.5 Isomerism
918Conformational isomerism
918Geometrical isomerism
919Optical isomerism
919Ionization isomerism
920Linkage isomerism
920Coordination isomerism
920Polymerization isomerism
921Ligand isomerism
92119.6
The Coordinate Bond
92119.7
Organometallic Compounds
92419.7 .1
Monohapto ligands
92519.7 .2
Dihapto ligands
93019.7 .3
Trihapto ligands
93319.7 .4
Tetrahapto ligands
93519.7 .5
Pentahapto ligands
93719.7 .6
Hexahapto ligands
94019.7 .7
Heptahapto and octahapto ligands
941
Chapter 20
Scandium, Yttrium, Lanthanum and Actinium
94420 .1 Introduction
94420.2
The Elements
94520.2 .1
Terrestrial abundance and distribution
94520.2.2
Preparation and uses of the metals
94520.2.3
Properties of the elements
94620.2.4
Chemical reactivity and trends
94820.3
Compounds of Scandium, Yttrium, Lanthanum and Actinium
94920.3 .1
Simple compounds
94920.3 .2 Complexes
95020.3 .3
Organometallic compounds
953
Chapter 21
Titanium, Zirconium and Hafnium
95421 .1 Introduction
95421 .2
The Elements
95521 .2 .1
Terrestrial abundance and distribution
95521 .2 .2
Preparation and uses of the metals
95521 .2 .3
Properties of the elements
95621 .2 .4
Chemical reactivity and trends
95821 .3
Compounds of Titanium, Zirconium and Hafnium
96121 .3 .1
Oxides and sulfides
961
XIV Contents
21 .3 .2
Mixed (or. complex) oxides21 .3 .3 Halides21.3 .4
Compounds with oxoanions21.3 .5 Complexes
Oxidation state IV (do)Oxidation state III (d')Lower oxidation states
21 .3 .6
Organometallic compounds
Chapter 22
Vanadium, Niobium and Tantalum22 .1 Introduction
97622.2
The Elements
97722.2 .1
Terrestrial abundance and distribution
97722.2 .2
Preparation and uses of the metals
97722.2.3
Atomic and physical properties of the elements
97822.2 .4
Chemical reactivity and trends
97922.3
Compounds of Vanadium, Niobium and Tantalum
98122.3 .1 Oxides
98122.3 .2 Polymetallates
98322.3 .3
Sulfides, selenides and tellurides
98722.3 .4
Halides and oxohalides
98822.3 .5
Compounds with oxoanions
99322.3 .6 Complexes
994Oxidation state V (do)
994Oxidation state IV (d')Oxidation state III (d2)
994Oxidation state II (d3)
99622.3 .7
The biochemistry of vanadium
99822.3 .8
Organometallic compounds
999999
Chapter 23
Chromium, Molybdenum and Tungsten
100223 .1 Introduction23.2
The Elements23 .2 .1
Terrestrial abundance and distribution23 .2 .2
Preparation and uses of the metals23 .2 .3
Properties of the elements23 .2 .4
Chemical reactivity and trends23.3
Compounds of Chromium, Molybdenum and Tungsten23 .3.1 Oxides23 .3 .2 Isopolymetallates23 .3 .3 Heteropolymetallates23 .3 .4
Tungsten and molybdenum bronzes23 .3 .5
Sulfides, selenides and tellurides23 .3 .6
Halides and oxohalides23 .3 .7
Complexes of chromium, molybdenum and tungstenOxidation state VI (do)Oxidation state V (dl)Oxidation state IV (d 2 )Oxidation state III (d3 )Oxidation state II (d4 )
23 .3 .8
Biological activity and nitrogen fixation23 .3 .9
Organometallic compounds
Chapter 24
Manganese, Technetium and Rhenium24 .1 Introduction24 .2
The Elements
962964966967967969971972
976
100210031003100310041005100710071009101310161017101910231023102410251027103110351037
104010401041
Contents
xv
24.2 .1
Terrestrial abundance and distribution
104124.2 .2
Preparation and uses of the metals
104124.2.3
Properties of the elements
104324.2 .4
Chemical reactivity and trends
104424.3
Compounds of Manganese, Technetium and Rhenium
104524.3 .1
Oxides and chalcogenides
104524.3 .2 Oxcanions
104924.3 .3
Halides and oxohalides
105124.3 .4
Complexes of manganese, technetium and rhenium
1054Oxidation state VII (dO)
1054Oxidation state VI (d')
1055Oxidation state V (d2 )
1055Oxidation state IV (d3 )
1056Oxidation state III (d 4 )
1057Oxidation state II (d 5 )
1058Lower oxidation states
106124.3 .5
The biochemistry of manganese
106124.3 .6
Organometallic compounds
1062
Chapter 25
Iron, Ruthenium and Osmium 107025 .1 Introduction
107025.2
The Elements Iron, Ruthenium and Osmium
107125.2 .1
Terrestrial abundance and distribution
107125.2 .2
Preparation and uses of the elements
107125.2 .3
Properties of the elements
107425.2 .4
Chemical reactivity and trends
107525.3
Compounds of Iron, Ruthenium and Osmium
107925.3 .1
Oxides and other chalcogenides
107925.3 .2
Mixed metal oxides and oxoanions
108125.3.3
Halides and oxohalides
108225.3 .4 Complexes
1085Oxidation state VIII (dO)
1085Oxidation state VII (d')
1085Oxidation state VI (d2 )
1085Oxidation state V (d 3 )
1086Oxidation state IV (d4 )
1086Oxidation state III (d 5 )
1088Oxidation state II (db)
1091Mixed valence compounds of ruthenium
1097Lower oxidation states
109825.3 .5
The biochemistry of iron
1098Haemoglobin and myoglobin
1099Cytochromes
1101Iron-sulfur proteins
110225.3 .6
Organometallic compounds
1104Carbonyls
1104Carbonyl hydrides and carbonylate anions
1105Carbonyl halides and other substituted carbonyls
1108Ferrocene and other cyclopentadienyls
1109
Chapter 26
Cobalt, Rhodium and Iridium
111326 .1 Introduction
111326.2
The Elements
111326.2 .1
Terrestrial abundance and distribution
111326.2 .2
Preparation and uses of the elements
111426.2 .3
Properties of the elements
111526.2 .4
Chemical reactivity and trends
111626.3
Compounds of Cobalt, Rhodium and Iridium
1117
XVI
26.3 .1
Oxides and sulfides26.3 .2 Halides26 .3 .3 Complexes
Oxidation state IV (ds)Oxidation state 111 (db)Oxidation state II (d7 )Oxidation state I (d8 )Lower oxidation states
26.3 .4
The biochemistry of cobalt26.3 .5
Organometallic compoundsCarbonylsCyclopentadienyls
Contents
Chapter 27
Nickel, Palladium and Platinum27 .1 Introduction27 .2
The Elements27 .2 .1
Terrestrial abundance and distribution27.2.2
Preparation and uses of the elements27.2.3
Properties of the elements27.2.4
Chemical reactivity and trends27 .3
Compounds of Nickel, Palladium and Platinum27 .3 .1
The Pd/H2 system27 .3 .2
Oxides and chalcogenides27.3 .3 Halides27.3 .4 Complexes
Oxidation state IV (db)Oxidation state III (d7 )Oxidation state II (d8 )Oxidation state I (d9 )Oxidation state 0 (d 10 )
27 .3 .5
The biochemistry of nickel27 .3 .6
Organometallic compoundsor-Bonded compoundsCarbonylsCyclopentadienylsAlkene and alkyne complexesn-Allylic complexes
111711191121112111221129113311371138113911401143
1144
11441145114511451148114911501150115111521154115411551156116611661167116711671168117011701171
Chapter 28
Copper, Silver and Gold
117328 .1 Introduction28.2
The Elements 1173117428.2.1
Terrestrial abundance and distribution
1 17428.2.2
Preparation and uses of the elements
117428.2.3
Atomic and physical properties of the elements
117628.2.4
Chemical reactivity and trends
117728.3
Compounds of Copper, Silver and Gold
118028.3 .1
Oxides and sulfides
118128.3 .2
High temperature superconductors
118228.3 .3 Halides118328 .3 .4 Photography
118528.3 .5 Complexes1187Oxidation state III (d$)
1187Oxidation state II (d9)
1189Electronic spectra and magnetic properties of copper(II)
1193Oxidation state I (dto) 1194Gold cluster compounds
119728.3 .6
Biochemistry of copper
119728.3 .7
Organometallic compounds
1199
Chapter 29
Zinc, Cadmium and Mercury
Contents
29 .1 Introduction29 .2 The Elements
29 .2 .1
Terrestrial abundance and distribution29 .2 .2
Preparation and uses of the elements29 .2 .3
Properties of the elements29 .2 .4
Chemical reactivity and trends29 .3
Compounds of Zinc, Cadmium and Mercury29 .3 .1
Oxides and chalcogenides29 .3 .2 Halides29 .3 .3 Mercury(I)
Polycations of mercury29 .3 .4
Zinc(II) and cadmium(II)29 .3 .5 Mercury(II)
Hgit -N compoundsHgtt-S compoundsCluster compounds involving mercury
29.3 .6
Organometallic compounds29.3 .7
Biological and environmental importance
Chapter 30
The Lanthanide Elements (Z - 58-71)
122730.1 Introduction30.2
The Elements30.2 .1
Terrestrial abundance and distribution30.2 .2
Preparation and uses of the elements30.2 .3
Properties of the elements30.2 .4
Chemical reactivity and trends30.3
Compounds of the Lanthanides30.3 .1
Oxides and chalcogenides30.3 .2 Halides30.3.3
Magnetic and spectroscopic properties30.3 .4 Complexes
Oxidation state IVOxidation state IIIOxidation state II
30 .3.5
Organometallic compoundsCyclopentadienides and related compoundsAlkyls and aryls
xtrü
1201120112021202120212031205120812081211121312141215121712181220122012211224
12271229122912301232123512381238124012421244124412451248124812481249
Chapter 31
The Actinide and Transactinide Elements (Z - 90-112)
125031 .1 Introduction
1250Superheavy elements
125331 .2
The Actinide Elements
125331 .2.1
Terrestrial abundance and distribution
125331 .2.2
Preparation and uses of the actinide elements
1255Nuclear reactors and atomic energy
1256Nuclear fuel reprocessing
126031 .2 .3
Properties of the actinide elements
126231 .2 .4
Chemical reactivity and trends
126431 .3
Compounds of the Actinides
126731 .3 .1
Oxides and chalcogenides of the actinides
126831 .3 .2
Mixed metal oxides
126931 .3 .3
Halides of the actinide elements
126931 .3 .4
Magnetic and spectroscopic properties
127231 .3 .5
Complexes of the actinide elements
1273Oxidation state VII
1273Oxidation state VI
1273Oxidation state V
1274Oxidation state IV
1275
xviii
Contents
Oxidation state 111
1277Oxidation state 11
127831 .3 .6
Organometallic compounds of the actinides
127831 .4
The Transactinide Elements
128031 .4 .1 Introduction
128031 .4 .2 Element 104
128131 .4 .3 Element 105
128231 .4 .4 Element 106
128231 .4 .5
Elements 107, 108 and 109
128331 .4.6 Elements 110, 111 and 112
1283
Appendix 1
Atomic Orbitals
Appendix 2
Symmetry Elements, Symmetry Operations and Point GroupsAppendix 3
Some Non-SI Units
Appendix 4
Abundance of Elements in Crustal RocksAppendix 5
Effective Ionic RadiiAppendix 6
Nobel Prize for Chemistry
Appendix 7
Nobel Prize for PhysicsIndex
1285
1290
1293
1294
1295
1296
1300
1305
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