Index 2017 PDF

Index
‘Note: Page numbers followed by “f” indicate figures and “t” indicate tables.’
A Black-body radiation, 3 alkene polymerization with Ziegler-

Abzymes, 209 p bonding, 104e107, 105f Natta catalyst, 217e218
Alkene complexes, 205e207, s bonding, 53e55 defined, 209
205fe206f Bonding theories heterogeneous catalysis, 217e218
Anionic complexes, 82e83 crystal field theory, 92e99 homogeneous catalysts, 209e211
Arene complexes, 107e111, 108fe111f distortions, 98e99 hydrogenation catalysts, 212e215
Aromatic complexes, 207, 207f experimental evidence stabilization, olefin metathesis with Grubbs/Schrock
Auranofin, 232, 232f 94, 94f catalysts, 220
geometries complexes, 95e96 Sonogashira cross-coupling reaction, 218
B octahedral complexes, 92e94, 93f, SuzukieMiyaura cross-coupling
Back p bonding, 78 94t, 97e98, 98t reaction, 218
Base hydrolysis, 140e143, 143t predictions, 97e98 Center of inversion, 36
Bent geometries, 20f spin pairing complexes, 97e98 CFSE. See Crystal field stabilization
Benzene sandwich complexes, square planar complexes, 96, 96f, 98 energy (CFSE)
112e114, 113fe114f stabilization energy, 96e99, 97t Characters of matrices, 49
BF3, 61e63, 62f tetrahedral complexes, 95, 95f, 98 Character tables, 50e51, 50t
Bidentate ligands, 79 trigonal bipyramidal field, 96 Charge transfer spectra, 168e170, 169f
Bioinorganic chemistry/applications, 225 metal complexes, 89 Chlorophyll, 76
biomineralization, 246e247, 246f molecular orbital (MO) theory, Cisplatin/cancer treatments, 228
cisplatin and cancer treatments, 228 99e114 anticancer platinum metallodrugs
anticancer platinum metallodrugs arene complexes, 107e111, carboplatin, 229, 229f
carboplatin, 229, 229f 108fe111f ferrocifen, 230e231, 231f
ferrocifen, 230e231, 231f arene-like ligands, 112, 112f formation, 228e229
formation, 228e229 benzene sandwich complexes, K1019, 230, 231f
K1019, 230, 231f 112e114, 113fe114f (N)KP1339, 230, 231f
(N)KP1339, 230, 231f p bonding, 104e107, 105f NAMI-A, 230, 231f
NAMI-A, 230, 231f effective atomic number (EAN) rule, square planar structure, 228, 228f
square planar structure, 228, 228f 106e107, 106fe107f titanocene chloride, 230, 230f
titanocene chloride, 230, 230f octahedral complexes, 100e102, Cluster chemistry
diagnostic metallodrugs, 233e234, 100fe101f, 101t, 104e107, 105f boranes, 172e179
233f square planar complexes, boron clusters bonding, 174e176,
metal ions, transport and storage, 104, 104f 174fe176f
234e235 tetrahedral complexes, 102e103, carboranes, 172e179
iron storage, 235e237, 235f 102f, 102t, 103f overview, 171
siderophores, 237e239, 238f valence bond theory, 90e92 polyhedral boron clusters, 172, 172fe173f
sodium-potassium pump, 239e240, coordination compounds, 90 Wade’s rules, 176e179, 177f,
240fe241f coordination number four, 91e92 177te178t, 179f, 179t, 180f,
oxygen transport and activation coordination number six, 90e91 182e194, 183f, 183t
proteins, 240e241 Bridging carbonyl, 203e205 capping groups, 185e186, 186f
hemocyanin, 245e246, 245f Bridging complexes, 83 condensed clusters, 186e187,
hemoglobin, 241e243, 242fe243f 186fe187f
myoglobin, 243e244, 244f C elements and transition metals,
salvarsan, 226, 226f Catalytic olefin metathesis, 220, 221f 180e182
therapeutic applications, of organometallic Catalytic processes interstitial atoms, 188
compounds, 231e232, 232f acetic acid from CH3OH, 216e217, isolobal relationships, 188e193,
vitamin B12, 227, 227f 216f 188fe189f, 189t, 190fe193f
251
252 Index
Cluster chemistry (Continued ) substitution reaction mechanisms, spin selection rule, 156
mixed main group/transition metal 116e118 TanabeeSugano diagrams, 167, 168f
clusters, 184ee185, 184f, 185t associative mode, 116e117, 116f tetrahedral (Td) complexes, 157e158,
noble gas structures, 193e194, 193f dissociative mode, 117e118, 118f 157t
Zintl anions, 180e182, 181f Coordination compounds vibronic coupling, 156
Cobalt carbonyl, 215 International Union of Pure and Electron spineintrinsic properties, 5e6
Complementary color, 89 Applied Chemists (IUPAC) rules, Electron transfer reactions, 145e149
Complex ions, 75e76 80e81
Coordination chemistry, 199 nomenclature, 80e83 F
activation parameters Coordination number ¼ 4, 84e87, Fe(CO)5, 107
activation volume, 121 84fe86f, 87f Five-coordinate complexes, 127e129,
enthalpy and entropy of activation, Coordination sphere, 115 129f
119e121 Core electrons, 7 Four-coordinate complexes, 126e127
mechanistic studies, 121e123, 122t Cr(CO)6, 107
Crystal field stabilization energy
coordination numbers reactions, G
123e149 (CFSE), 96e99, 97t
Gouy balance, 89
base hydrolysis, 140e143, 143t Crystal field theory, 92e99
Group symmetry orbitals, 52
electron transfer reactions, 145e149 crystal field stabilization energy
Group theory
five-coordinate complexes, 127e129, (CFSE), 96e99, 97t
cyclopentadienide ion, 64, 64f
129f distortions, 98e99
molecular spectroscopy
four-coordinate complexes, experimental evidence stabilization, 94,
symmetry normal modes, 65e69,
126e127 94f
66f, 67t, 68f
group 13 tetrahedral complexes, 126, geometries complexes, 95e96
types, 65
126t octahedral complexes, 92e94, 93f, 94t,
vibration normal modes, 65e69, 66f,
group 14 tetrahedral complexes, 97e98, 98t
67t, 68f
126e127 predictions, 97e98
molecular structure
heavier group 9 metals, 144, spin pairing complexes, 97e98
BF3, 61e63, 62f
144te145t square planar complexes, 96, 96f, 98
molecular orbital correlation dia-
inner sphere mechanism, 145e147, tetrahedral complexes, 95, 95f, 98
gram, 61e63
146f trigonal bipyramidal field, 96
quantum mechanics, application to,
isomerization during substitution, 51e53
139e140 D triangular planar structure, 53e61,
kinetic effect, 133, 133f Direct product, 52 54fe55f, 56t, 57fe61f
outer sphere mechanisms, p orbitals, 64
147e149 E overview, 43
phosphorus, 127e129, 127f Effective atomic number (EAN) rule, square planar ML4, 63e64
six-coordinate octahedral complexes, 106e107, 106fe107f, 201 symmetry operations properties,
134e139, 135t, 137t, 138f, 138t, Electroneelectron repulsion, 7e8 43e51
139f, 139t Electronic spectra character tables, 50e51, 50t
square planar complexes, 129e132, charge transfer spectra, 168e170, 169f irreducible representations, 48e50,
130te131t La Porte selection rule, 156 50t
sulfur, 127e129 molar absorptivity, 156e157 reducible representations, 48e50, 50t
three-coordinate complexes, octahedral (Oh) complexes, 157e158, representations, 46e48, 46t, 47f
123e125, 124te125t 157t sequential operations, 43e46,
trans effect, 132e133, 132f Orgel diagrams, 158e167, 158f 44fe45f, 45t
two- to six-coordinate complexes, distortion effect, 160, 160f
123, 123t
metal complexes complications
F states systems, 160e167, H
161fe162f, 165fe166f Heavier group 9 metals, 144, 144te145t
complex ligands, 119, 120t simple one-electron approach, 159 Heme group, 75
solvent competition, 119 overview, 155 Heterogeneous catalysis, 217e218
overview, 115 selection rules, 155e157 Homogeneous catalysis, 76
Index 253
insertion reaction, 211 coordination compounds, 77e78 square planar complexes, 104, 104f
oxidative addition and reductive electronic structures, 76e77, 76t tetrahedral complexes, 102e103, 102f,
elimination, 209e211, 210f Lewis bases, 78e80, 80f 102t, 103f
Hund’s rules, 11 ligands, 78e80, 79f Molecular spectroscopy
Hydroformylation, 214e215, 215f molecular structure, 78f symmetry normal modes, 65e69, 66f,
Hydrogenation catalysts oxidation states, 76e77, 77t 67t, 68f
hydroformylation, 214e215, 215f Linear geometries, 21f types, 65
monohydride complexes, 213, 214f vibration normal modes, 65e69, 66f,
types, 212 M 67t, 68f
Wilkinson’s catalyst Magnetic moment, 89 Molecular structure
characteristics, 213 Magnetic properties, 5 BF3, 61e63, 62f
higher coordinated solvo-complex Magnetic susceptibility, 89 molecular orbital correlation diagram,
formation, 213, 213f Many electron atom, 6e8 61e63
mechanism, 212, 212f Matrix representations, 46e48 quantum mechanics, application to,
Metal carbonyls, 205t 51e53
I Co2(CO)8, electronic arrangement/ triangular planar structure, 53e61,
Improper axes of rotation, 36 possible two structures, 202e205, 54fe55f, 56t, 57fe61f
Infrared (IR) active, 68 203fe204f Molecular symmetry
Inner sphere mechanism, 145e147, Fe(CO)5, electronic arrangement of, elements, 32e34
146f 202, 202f operations, 31e32, 32f
Insertion reaction, 211 Mn2(CO)10, electronic arrangement/ symmetry operations, 31e32
International Union of Pure and Applied structure of, 203e205, 203f examples, 35e38
Chemists (IUPAC) rule, 80e81 multimetal carbonyl complexes, operations, 32e34
Iron storage possible isomeric structures, overview, 31
ferritin, 236e237, 237f 203e205, 204f PBr5, 35, 35f
transferrin, 235e236, 235f Ni(CO)4, electronic arrangement of, PF2Cl3, 37, 37f
Irreducible representations, 48e50, 50t 202, 202f point groups, 38e42
Isomer, 37 Mirror planes, 36 assigning rules, 39
Isomerism, 84e87 Molar absorptivity, 156e157 examples, 39e42, 40t
Isomerization during substitution, Molecular geometries symmetry, 41t
139e140 nonrigid shapes of molecules Monoclonal antibodies, 209
general concept, 26 Monodentate ligands, 78
J specific examples, 27e30 Monohydride complexes, 213, 214f
JahneTeller distortion, 99 overview, 15
shapes of molecules N
K other considerations, 25e26 Naming complex cations,
specific examples, 19e25, 19f 81e83
Kinetic effect, 133, 133f
valence shell electron pair repulsion Neutral complexes, 81e83
(VSEPR) model, 16e18 n-fold improper axis of rotation, 34
L Molecular motion, 65 Niels Bohr’s model, 3
Lewis acid, 77
Molecular orbital correlation diagram, Normal modes, 65e69
Ligands and metal complexes
61e63
coordination compounds
International Union of Pure and
Molecular orbital (MO) theory, 99e114 O
arene complexes, 107e111, 108fe111f Octahedral complexes, 18, 18f, 22f,
Applied Chemists (IUPAC) rules,
arene-like ligands, 112, 112f 85e87, 100e102, 100fe101f,
80e81
benzene sandwich complexes, 101t, 104e107, 105f, 157e158,
nomenclature, 80e83
112e114, 113fe114f 157t
isomerism, 84e87
p bonding, 104e107, 105f Olefin metathesis, 220, 221f
coordination number ¼ 4, 84e87,
effective atomic number (EAN) rule, Order of the group, 46
84fe86f, 87f
106e107, 106fe107f Organometallic chemistry, 199
overview, 75e76
octahedral complexes, 100e102, Organometallic compounds, 199
transition metals, 76e80
100fe101f, 101t, 104e107, 105f
254 Index
Organometallic compounds (Continued ) spineorbit coupling, 11e13, 12f T

alkene complexes, 205e207, valenceevalence repulsion, 8e11 TanabeeSugano diagrams, 167, 168f
205fe206f overview, 3 Term symbols, 10
aromatic complexes, 207, 207f Tetradentate ligands, 79e80
effective atomic number rule, 201 R Tetrahedral complexes, 17, 17f, 20f, 84,
IUPAC nomenclature, 201, 201f Reducible representations, 48e50, 50t 102e103, 102f, 102t, 103f,
metal carbonyls, 205t Reduction equation, 56 157e158, 157t
Co2(CO)8, electronic arrangement/ Reduction formula, 49e50 Three-coordinate complexes, 123e125,
possible two structures, 202e205, Representations, 46e48, 46t, 47f 124te125t
203fe204f Rotational motion, 65 Titanocene chloride, 230, 230f
Fe(CO)5, electronic arrangement of, Total orbital angular momentum, 8e9
202, 202f S Total spin angular momentum,
Mn2(CO)10, electronic arrangement/ SALC. See Symmetry Adapted Linear 9e10
structure of, 203e205, 203f Combinations (SALC) Trans effect, 132e133, 132f
multimetal carbonyl complexes, Salvarsan, 226, 226f Transferrin, 235e236, 235f
possible isomeric structures, Sandwich compounds, 207 Transition metal complex, 115
203e205, 204f Schrock catalysts, 220, 221f Transition metals, 76e80
Ni(CO)4, electronic arrangement of, Seesaw, 21f coordination compounds,
202, 202f Sequential operations, 43e46, 44fe45f, 77e78
therapeutic applications, 231e232, 45t electronic structures, 76e77, 76t
232f Siderophores, 237e239, 238f Lewis bases, 78e80, 80f
types of, 200, 200f Silver sulfadiazine, 232, 232f ligands, 78e80, 79f
Orgel diagrams, 158e167, 158f Six-coordinate octahedral complexes, molecular structure, 78f
distortion effect, 160, 160f 134e139, 135t, 137t, 138f, oxidation states, 76e77, 77t
F states systems, 160e167, 161fe162f, 138t, 139f, 139t Triangular planar structure, 53e61,
165fe166f Sodium-potassium pump, 239e240, 54fe55f, 56t, 57fe61f
simple one-electron approach, 159 240fe241f Tridentate ligands, 79
Outer sphere mechanisms, Sonogashira cross-coupling reaction, Trigonal bipyramidal, 17, 17f, 21f
147e149 218, 219f Trigonal planar, 16, 16f
Oxidative addition/reductive Spineorbit coupling, 11e13, 12f Trigonal prism, 18, 18f
elimination, 209e211, 210f Square planar complexes, 84e85, 104, Trigonal pyramid, 20f
104f, 129e132, 130te131t Tripodal ligand, 79e80
P Square planar geometries, 22f T-shaped, 21f
Pauli’s exclusion principle, 9 Square planar ML4, 63e64 Two- to six-coordinate complexes, 123,
Penta- and hexadentate ligands, 80 Square pyramid, 22f 123t
Phosphorus, 127e129, 127f Sulfur, 127e129
Polydentate ligands, 78e79 Suzuki-Sonogashira coupling, 199, 218, V
Polytopal isomerization, 28 219f Valence bond theory, 90e92
Projection formula, 53 Symmetry Adapted Linear coordination compounds, 90
Pseudorotation mechanism, 28f Combinations (SALC), 52 coordination number four, 91e92
Pyrrole groups, 75 Symmetry normal modes, 65e69, 66f, coordination number six, 90e91
67t, 68f Valence electrons, 7
Q Symmetry operations properties, 43e51 Valence shell electron pair repulsion
Quantum mechanics, 51e53 character tables, 50e51, 50t (VSEPR) model, 16e18
Quantum theory irreducible representations, 48e50, 50t Valenceevalence repulsion, 8e11
hydrogen atom, 3e13 reducible representations, 48e50, 50t Vibrational motion, 65
electroneelectron repulsion, 7e8 representations, 46e48, 46t, 47f Vibration normal modes, 65e69, 66f,
many electron atom, 6e8 sequential operations, 43e46, 44fe45f, 67t, 68f
quantum numbers and significance, 45t Vibronic coupling, 156
4e6, 5f, 6t Syphilis, 226 Vitamin B12, 76, 227, 227f
Index 255
VSEPR model. See Valence shell elements and transition metals, higher coordinated solvo-complex
electron pair repulsion (VSEPR) 180e182 formation, 213, 213f
model interstitial atoms, 188 mechanism, 212, 212f
isolobal relationships, 188e193,
W 188fe189f, 189t, 190fe193f Z
Wade’s rules, 176e179, 177f, mixed main group/transition metal Zero-order approximation, 6e7
177te178t, 179f, 179t, 180f, clusters, 184e185, 184f, 185t ZieglereNatta catalyst, 217e218,
182e194, 183f, 183t noble gas structures, 193e194, 193f 217fe218f
capping groups, 185e186, 186f Wilkinson’s catalyst ZieglereNatta polymerization, 199
condensed clusters, 186e187, characteristics, 213 Zintl anions, 180e182, 181f
186fe187f

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A Black-body radiation, 3 alkene polymerization with Ziegler-

Organometallic compounds (Continued ) spineorbit coupling, 11e13, 12f T

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