INDEX

1,2-addition 505, 531, 533–534

accumulation layer 569

acetonitrile complexes 352–353, 367

acidity of H2 ligand 195–199

acrylic acid 265, 266

actinide complexes 365

activation barrier, kinetic barrier 439, 469

activation energy 560

activation enthalpy 123, 133, 138, 151, 152,

155, 156, 162

activation entropy 123, 133, 138, 151, 152,

155, 156

activation volume 123

adiabatic 5, 13, 15

agostic 495–500, 529

alkane 496–498, 500–503, 506, 510–515,

529, 532, 539, 541–544

alkane coordination 541

alkynes 251, 265, 266, 268, 269

aluminum(III) complexes 355–357,

364–365, 383, 383–386

ammonia (anhydrous liquid) 369

anagostic 498

antennae 559

aromatic 506, 509–511, 528–530, 539, 543

hydroxylation 161

ascorbic acid 274

aspirin 252

associative electron transfer 406

associative mechanism 343–346, 353–354,

368, 378–381, 387

atmosphere 247, 274

B3LYP 472, 475, 478, 479, 481, 483, 486

backbonding 498, 510, 542

back-donation (BD) from metal to H2 193,

195, 215, 217, 224, 225

Badger’s rule 135

Basolo, Fred 339, 342, 358–359, 373, 379

1-benzyl-1,4-dihydronicotinamidne

(BNAH) 44, 47, 63, 65, 67

beryllium complexes 355–357, 366

bicarbonate 256, 257, 261

biomass 247

bipyridine 60, 552, 553, 560, 572, 581

bis(m-oxo)dicopper(III) complexes 163,

178

bisphenol A 264, 265

bleomycin 166

BLYP/6–31G** 48

bond dissociation energy (bde) 39, 67, 68,

459, 465, 480, 486, 487, 495–496,

511, 517

of O2 110

bond lengths 250

bonding in H2 complexes, 189–193, 195,

209, 215–220, 225

s-bondmetathesis 505, 518, 521–531, 535,

537–538

Bosch-Meiser process 252, 263

Bouduard reaction 271

BP86 475, 478, 480, 484, 486, 487

bromoperoxidase 83

Brønsted base 47

butadiene 268, 269, 270, 271, 481

butenoic acids 266

cage escape 576

calculations 516, 523, 525, 527, 530,

535–59

Physical Inorganic Chemistry: Reactions, Processes, and Applications Edited by Andreja BakacCopyright � 2010 by John Wiley & Sons, Inc.

589

calorimetry 454, 465, 481

carbamate 266, 268

carbonate rocks 247

carboxylation 248, 265

carboxylic acids 265, 266, 273

catalyst 495, 518, 545

charge recombination 577, 580

charge separation 562, 564, 575, 582

charge transfer 552

complex 40

chelate effect 376–377

chlorate 85, 100

chlorite 83

chlorite dismutase 83–83

chloro-p-benzoquinone 53

chloroperoxidase 82

chromium carbonyl 478–480

chromium(II) complexes 355, 362–363

chromium(II) compounds 142

chromium(III) complexes 349–352, 355,

359, 361, 367, 369–375

cis ligand effect 372–373

CISD 475

cisplatin 364, 377

CO exchange 475

cobalt 102

cobalt carbonyls 484–487

cobalt compounds 146

cobalt(II) aqua complexes 347, 355–356

cobalt(III) am(m)ine complexes 340, 342,

351, 353, 360–361, 369–375, 382,

387

cobalt(III) aqua complexes 340–341,

346–347, 353, 355, 360, 362, 369, 382

colligation 403

collision distance 20, 23, 24

collision rates 1, 2

colloids 274

compressed hydride 194, 195, 208

computer modeling of ligand

substitution 359, 363, 381–385, 387

conductance band 274

conjugate base mechanism 342, 349, 350,

352, 357, 364–365, 369, 371,

373–375

coordination modes of CO2 249, 250

copper complexes 136–140, 159–163

copper(II) complexes 355, 362–364

corrolazine 93–95

corrole 93–95

Coulombic work 7, 9

cyano complexes 341, 346–347,

377–379

cyclam macrocycle 102

cyclic carbonates 261, 262, 263, 273

cyclic voltammetry 53, 286, 329

cyclidenes 125–129

b-cyclodextrin 261, 263

cyclometalation 522, 525–526

cytochrome P450 75, 77–80, 164–165

CCSD 477

Davies equation 16, 19

DBU 259, 265

Debye-H€ukel equation 16

Debye-Smoluchowski model 3

delocalization 437, 458, 467, 468, 469

dendrimeric phosphines 274

dendrimers 158

density functional theory (DFT) 48, 256,

265, 266, 276, 475, 523, 527, 530,

535, 537–538

density of states 567, 568

deprotonation 68

deuterium 501, 512–513, 525, 531

deuterium complexes and substitution 190,

203, 207, 208, 209, 212, 214, 215,

230, 232–235

Dewar-Chatt-Duncanson bonding

model 193, 217

di(2-ethylheptyl)phtalate 269

diffusion-controlled collision 3

dihydrogen bonding 192, 226

dihydrogen complex 189–237

dihydronicotinamide adenine dinculeotide

(NADH) 42, 43, 47, 57, 63, 64,

65, 67

dimerization 396, 443, 457, 461, 468, 469,

478

dimethyl carbonate 261, 262, 263, 268

10,100-dimethyl-9,90-biacridine [(AcrH)2] 481,1-dimethylferrocene [(C5H4Me)2Fc] 49,

50, 51

dimethylformamide complexes 349–351,

366–368, 375

dimethylsulfoxide complexes 366–367,

378

dinitrosyls 312, 313

590 INDEX

diode equation 581

dioxygen affinity 120, 123, 127, 128, 129,

132, 178

dioxygen binding rates 128, 129, 178

dioxygen carriers 116, 117, 121

diphenylcarbonate 261, 263, 265

dipole moment 554

discrete variable representation (DVR)

analysis 219, 220, 235

disproportionation 61, 398

dissociative electron transfer 406

dissociative mechanism 343, 346–347,

353–354, 366, 368, 378–379, 387

dithiolene 560

DMC 261, 263, 264, 273

DMF 258, 259, 260, 266

dppe 255, 258, 259, 266

dynamic behavior of H2 complexes 190,

193–195, 197, 204, 208, 224

early transition metal 523, 531

eclipsed conformer 479

electrochemical reduction of CO2 248, 251,

272, 273, 274

electron correlation 475

electron coupling element (HDA) 40, 44

electron energy loss spectroscopy 213, 215

electron self-exchange 10, 22

electron transfer 429, 432, 443, 447, 455,

456, 459, 468

electronic coupling 14, 15

electrophilic addition at MNO 313

electrophilic substitution 505, 518,

528–530, 537

electrophilicity 61

elongated (stretched) H2 complexes 194,

195, 203, 207, 208, 213, 215, 217,

219, 220, 225, 235

energy gap law 554, 555

energy transfer 557, 558

enthalpy of activation 340, 352–353, 355,

360–361, 366–368, 387, 447, 451,

452, 454, 455, 461, 469, 475–477,

496

entropy effects in H2 binding 231, 234

entropy of activation 345, 352–353, 355,

361, 366–368, 387, 451, 455, 460,

462, 469

epoxidation 175–176

EPR (ESR) spectroscopy 48, 49, 53, 57, 59,

60, 284, 487

S ¼ 3/2,1/2 nitrosyls, n ¼7 303, 306

g values for cyanonitrosyls 304

spin densities 304, 305

5-coordinate nitrosyls 307

metallonitrosyl porphyrins 328

equilibrium isotope effect 230–233

Escherichia coli taurine 62

Et3N 260, 274

excited state 560, 571, 575

extinction coefficient 560

Eyring equation 9

fast IR spectroscopy 541

ferrocene-quinone dyad 50

ferryl intermediates 141, 144, 165, 175

force constants for M–H2 215–219, 232,

233, 235

formaldehyde 251, 253, 254, 257, 273

formamides 253, 254, 258, 259

formate esters 253, 254, 259, 260

formic acid 248, 251, 253, 254, 255, 256,

257, 258, 259, 260, 261, 272, 273

four-electron dioxygen reduction 115,

163–164

Franck-Condon 554, 563, 566

Franck-Condon Principle 5

free energy 524

free energy of activation 357

free energy relationships 369–371

gallium(III) complexes 356–357, 386

general gradient approximation (GGA) 475

geochemical applications 383–388

Gerischer 566, 568

Gibbs energy change 44

glycerol carbonate butyrate (GCB) 271

glycerol carbonate propionate (GCP) 271

gold(III) complexes, 344, 358, 378–379,

387

Gray, H. B. 343–345

greenhouse effect 247

Guggenheim equation 17, 19

halogenase CytC3 62

Hammett correlation 139, 175

hard sphere model 9, 20

Hartree–Fock (HF) theory 474

INDEX 591

HAT 408

hemerythrin 118–120, 121, 148

hemicolligation 402

hemocyanin 118, 120

hemoglobin 117

heteroleptic 560

heterolytic cleavage of dihydrogen 191,

192, 195–201, 230

histidine 48, 49, 50

hot carrier 574

hydrazine 301

as a nucleophile with SNP 301

catalytic cycle for reduction of

nitrite 301

methyl-substituted derivatives 303

hydride abstraction 174, 175, 179

hydride complex 189–203, 205, 206, 208,

209, 211, 215, 219, 222–224,

230–237

hydride transfer 57, 58

hydrogen 101

hydrogen atom abstraction 174, 175, 179

hydrogen binding to porous materials 223,

226–229

hydrogen bond 255

hydrogen bonding 41, 47, 53, 54, 70

hydrogen chromate ion 69

hydrogen coordination and

activation 189–237

hydrogen peroxide 75, 79, 81, 102

hydrogen production 189, 191, 199–201

hydrogen storage 189, 191, 200, 222–226,

260

hydrogenases 197, 199

hydrogenation 189, 192, 196, 197–200248,

251, 253, 254, 255, 256, 257,

258, 260, 261, 269, 272, 273,

275

hydroperoxo 102–103

chromium 102, 103

complexes 169, 173

hydrosphere 247

hydroxyl radical production 401

hyperfine coupling 488

hyperfine coupling constants (hfc) 48, 49,

55, 57

hypophosphorus acid 100

indium(III) complexes 352, 356

inelastic neutron scattering 193, 200,

208–210, 213, 216, 224–229

inner sphere 8, 25

electron transfer 40

p-p interaction 41

interchange mechanisms 347–354, 356,

369–370, 375, 378, 380–381, 387

internuclear distance 17, 20, 22

inverse kinetic isotope effect 503, 514–516

inverted region 12

ion pairing 33, 348–352, 369, 378

IR frequencies for M–H2 209–221, 223,

226, 229, 235

IR spectroscopy 285, 287, 303, 317,

541–543

iridium 105

iridium(III) complexes 355, 360–361, 371,

374

iron 83–89, 77–81, 481–482

iron(II) complexes 355–356, 362, 367,

382

iron(III) complexes 341, 355–356, 357,

359, 367, 370–371

isokinetic temperature 156

isoprene 481

isotope effects 190, 191, 203, 207, 208,

230–237

Jablonski diagram 554

Jahn–Teller effect 358, 477, 487

Keggin heteropolytungstate 21, 22, 32

ketene complex 478

2-ketoglutarate-dependent

enzymes 166–167

a-ketogultarate dioxygenase (TauD) 62

kinetic isotope effect (KIE) 39, 42, 44, 50,

59, 66, 67, 236–237, 471, 503,

508–509, 514–516, 531–532

kinetics 432, 440, 442, 448, 449, 450, 451,

452, 454, 465, 469

Kolbe-Schmitt synthesis 248, 251, 252, 265

lactone 251, 265, 266, 268

d-lactone 268, 269, 270, 271

Langford, C. H. 343–345, 369

lanthanide complexes 355, 357,

365–366, 368

laser flash photolysis 43, 44, 47

592 INDEX

late transition metal 505, 525–526, 528,

531, 534, 536–537, 539–540

Lewis acidity 55

ligand field 571

ligand field theory 357–365

ligand reactions of radicals 417

ligand substitution by radicals 411

ligand-centered radical 430, 467, 468, 469

linear free energy relationship (LFER) 10,

294, 296, 315

lipoxygenase 41

manganese carbonyls 480–481

manganese(II) complexes 355–356, 362,

367, 382

Marcus cross-relation (MCR) 6, 11, 26, 174

Marcus model 3, 19

Marcus theory 40

mass spectrometry 525–526

mechanisms of CH activation 504

mechanistic classification 341ff

MECP (minimum energy crossing

point) 471–474

metal ion aqua complexes 347–366, 371

metal ion-coupled electron transfer

(MCET) 41, 54, 55

metal-nitrosyl compounds 282, 285

bonding MO model 282, 284

Enemark-Feltham formalism 282,

284

coordination geometries 283, 285

linear MNO, n ¼ 6 286

preparative methods 286

partially bent MNO, n ¼7 303

dithiolene coordination 328

disproportionation of NO 312

reactions with dioxygen 313

EPR with 5- and 6-coordinate

porphyrins 308

non-innocent character 328

strongly bent, n¼ 8 (NO�, HNO) 285,

316

metal peroxides 168–169, 171–173, 179

metal superoxides 168, 170, 171, 179

metalloradical 505

metal-organic frameworks (MOFs) 200,

223, 226, 229

metal-oxo complexes 62, 140–144, 169,

173–178

metal-superoxo complexes 122, 132

methacrylic acid 266

methane 85, 251, 254, 265, 271, 272,

497–498, 502–504, 508, 512,

518–532, 537, 541–542

methane monooxygenase 167–168

methanol 248, 251, 254, 259, 260, 263, 271,

272, 273, 278

methanol complexes 367

10-methylacridone (AcrO) 66

10-methyl-9,10-dihydroacridine

(AcrH2) 42, 46, 47, 58, 59, 60, 61,

63, 64, 65, 66, 67, 68, 69

methyldioxorhenium (mdo) 100

methyl formate 259, 260

methylamine complexes 361, 374–375,

380, 382, 387

methyltrioxorhenium (mto) 96, 100

microscopic reverse 501, 515–516, 518,

520

minimum energy crossing point

(mecp) 471, 472, 474

molybdenum 89–93, 104

molybdenum(III) complexes 352, 371

Monte-Carlo 559

M€ossbauer spectroscopy 290, 306

zero-field parameters for n ¼ 6, 7

nitrosyls 291

application to nitrosyl-dithiolene

complexes 329, 332

MP2 472, 475

Mulliken population analysis 74

myoglobin 117

NO linkage isomers 318

differential Scanning Calorimetry 318

ground and excited states 319–320

X-ray, structural changes, MS1,

MS2 321

infrared and Raman evidence 322

N2O linkage isomers 302

N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)

methylamine (N4Py) 63, 64, 65

nanocrystalline 552

natural population analysis (NPA) 474, 486

N-benzyl-N,N’,N’-tris(2-pyridylmethyl)

ethane-1,2-diamine (Bn-TPEN) 63,

65

Nernstian 569

INDEX 593

neutron diffraction 193, 194, 201–203,

205–207, 217, 221

neutron spectroscopy 191, 201, 208–210,

213, 216, 224–229

nickel(II) complexes 352–353, 355, 359,

367, 369, 376–378, 382

nickelalactone 266

Ni complexes 266

nitrogen monoxide (NO) 281

biological significance 281

electronic configuration 281

reductive chemistry 282

as a ligand 285

ligand interchange 309

disproportionation 312

reaction with O2 316

pulse radiolysis 282

nitrosonium ligand (NOþ ) 281, 285

bonding 287

IR spectroscopy 287

UV-vis spectroscopy 287

theoretical calculations 289

addition of OH� 293

M€ossbauer spectroscopy 290, 291,

329

photoreactivity 323

preparative chemistry 286

nitrosyl porphyrins 290

NO-dissociations 290

nitrophorins 290, 292

electronic structure 292

EP 308

QM/MM calculations 292

nitroxyl ligand (NO�) 281, 285

protonated species, HNO 281, 285,

316

bonding model 284

preparative methods 316, 3171H NMR for Mb(HNO) 317

reactivity 316

NMR

spectroscopy 504, 521–522, 534, 541,

543–545

dipolar coupling 204

relaxation time 191, 205, 206

spectroscopy, deuterium 204

spectroscopy, solid state 191, 201, 203,

205, 217, 219

spectroscopy, solution 205, 206, 225

T1 205, 206

T1(min) 205

HD coupling 190, 205–208, 286, 329

NO addition 414

NO2�, NO and N2O reductases 281

nonadiabatic 15

nonaqueous solvents 366–369

noncovalent interactions 41

nonheme iron 145, 147, 175–176

non-heme iron enzymes 85–89

normal coordinate analysis of

M–H2 215–218

normal region 564

nuclear magnetic resonance

relaxation 352–353, 386

nuclear resonance vibrational spectroscopy

(NRVS). . . . 292

nuclear tunneling 5, 13

nucleophile-assisted electron transfer 416

nucleophilic addition at MNO. . . . 293

addition of OH�. Rates andmechanism 295, 296

coligands�ınfluence on reactivity 297

DFT calculation 299

addition of nitrogen hydride 301

nucleophilicity 342–343, 349–351, 379

O atom transfer 411

one-electron dioxygen reduction 114

one-electron reduction potential (Ered) 49,

53

orbital (sigma) 496–498, 510, 517–518,

523, 534, 538

organic azides 98

organic carbonates 248, 261, 263, 268, 271

osmium 76, 105

outer sphere 8, 25

oxazoline 98

oxidases 110

oxidative addition 501, 505–510, 512–528,

530, 542, 544

oxidative addition of hydrogen 189, 190,

194–196, 219, 223, 230, 234, 236, 237

oxidative hydrogen migration 526

oxidative quenching 562, 563

oxiranes 262, 263, 264

oxoanions as ligands 372–373, 377

oxoiron(IV) 62

oxotransferase 89–93

594 INDEX

oxygen 75, 79, 86, 102

oxygen atom transfer 174, 175, 179

oxygenases 110

oxygenation barriers 125

ozone 111, 144

Pake pattern 204

palladium 101

palladium(II) complexes 344, 355, 358,

364, 378–380, 387

p-benzoquinone 53

PCET 407

p-chloranil 64, 65, 66

Pearson, R. G. 339, 342, 358–359, 373

PEMFC 260

perchlorate 83, 99

perchlorate reductase 84

peroxidases 81–83

peroxide 112, 113, 115, 144

peroxo dimer formation 125

peroxo-diiron complexes 148, 149

peroxynitrite 324

preparative chemistry 324

O-bound and N-bound 315, 324

interactions with superoxide and

NO 325

metal complexes 325

NO2 radical intermediates 327

phenothiazine 580

phosphines 88

photochemical reduction of CO2 251, 261,

272, 273, 274

photochemical processes 200, 201, 214,

215, 220–222

photochemical reactivity of {MNO}n 323

photoelectrochemical 273

photoinduced ET 55

physisorption ofH2 189, 194, 200, 225–228

platinum(II) complexes 344–346, 355, 358,

364, 377–381, 387

PMe3 255, 258, 259, 260

point of zero charge 578

polyamine ligands 124

polycarbonates 248, 261, 263, 264, 265

polyoxometalates 385–387

polyurethanes 261, 266, 268

porphyrazine 94

porphyrin 80, 94, 140

porphyrin complexes 366

potential energy surface 3, 14, 195, 207,

208, 220, 221, 471, 472, 474, 476, 478

PPh3 250, 255, 258, 260, 268

prolyl-4-hydroxylase 62

propylene carbonate 261, 262, 263, 264

proton transfer 400

protonation reactions 192, 196, 197, 231,

237

proton-coupled electron transfer

(PCET) 41, 42, 66, 67, 68, 70, 174,

179

proximity effects 179

pseudo-first-order kinetics 50

pta 256, 257

pulsed time-resolved photoacoustic

calorimetry 480

pyrones 265, 268, 269

radical 505 – 508, 534

radical addition to metal ions 411

radical association 402

radical chain mechanism 69

radical clocks 78, 80

radical electron transfer 404

radical ion pair 53

radical nucleophilic displacement 404

radical oxidative cleavage 407

radicals 395

Raman spectra for M–H2 208, 209, 211,

212, 214–216, 219, 222

rate constants for dioxygen binding 124,

137, 138, 141, 152, 154

reaction rates 462, 471

reciprocal Debye radius 7, 20

redox non-innocent ligands 433, 467

redox potentials for oxygen

reduction 111–113

reductive cleavage by radicals 417

reductive cleavage of radicals 408

reductive coupling 501–502, 513–515, 517,

520

reductive elimination 500–503, 508,

513–520, 525

reductive nitrosation 419

reductive nitrosylation 286, 419

reductive quenching 562, 563, 575, 580

reforming 271, 272

relaxed PES scan 476

remote injection 555, 573

INDEX 595

reorganization energy 8, 576

reverse water gas shift reaction 254, 271

Rh 250, 255, 257, 260

rhenium 95–102

rhodium 102, 255, 256, 257

rhodium carbonyls 487–488

rhodium(III) complexes 355, 360–361,

371, 374–375

rotation of bound H2 195, 204, 205,

225–227, 229

rotational transition state 480

Ru 256, 257, 258, 259, 260, 261,

272, 274

Ru(IV)-oxo species 66

ruthenium carbonyls 482–484

ruthenium porphyrins 143–144

ruthenium(III) complexes 342, 355,

361–363, 371, 374

sacrificial electron donor 274

salicylic acid 248, 251, 252, 265

scandium(III) complexes 368

selectivity 349, 362, 370–371, 379,

387

silicate mineral dissolution 384

singly occupied molecular orbital

(somo) 435, 437, 467

Slater-type orbital (STO) 480, 484

Snamprogetti urea process 253

SOD 399

solar energy 275, 572, 582

solvatochromic 560

solvent exchange reactions 351–369

spectroelectrochemistry 328, 329

spin contamination 474

spin crossover, spin state change 465, 469,

470, 471, 472, 474

spin density 436, 467, 469, 474, 481,

483, 487

spin pairing 464, 465

spin-forbidden substitution 415

spin-orbit coupling 470, 471

staggered conformer 479

Stamicarbon urea process 253

stereochemistry of ligand

substitution 371–374

steric effects 374–375, 379–381

steric hindrance 459, 460, 461, 464, 465,

467, 468

stopped-flow 59

structural isotope effects 207

sulfides 88

supercritical 258, 260, 263, 268

superoxide 112, 113, 114, 115

superoxide binding 413

supramolecular 578

surface binding of H2 200, 212, 215, 223,

226, 228, 229

synthesis of dihydrogen

complexes 189–193, 196

task-specific ionic liquid 258, 262,

Taube, Henry 339, 340, 342, 351, 357–358,

362

telomerization 268, 269, 270

tetra-amido ligands 87

tetragonal distortion 477

tetragonal pyramidal structure 485

1,4,8,11-tetramethyl-1,4,8,11-

tetraazacyclotetradecane

(TMC) 62, 63, 65

tetrazine 42

thermodynamic oxygen transfer

potential 76

thermodynamics 252, 254

thermodynamics of ligand substitution

340

third-order radical kinetics 416

time dependent DFT (TDDFT) 289

titanium(III) complexes 355–356, 361

titanol 569

TMEDA 265

1-(p-tolylsulfinyl)-2,5-benzoquinone

(TolSQ) 48, 49

trans-effect 307

signaling role of NO in sGC 307

cyanide labilization in SNP 307

total reorganization energy 25

transmission coefficient 5, 9

trap states 568

triethanolamine 274

triethylamine 254, 258,

trimethylphosphate complexes 366,

368

Truncated Guggenheim equation 17, 18

T-shaped structure 485

tungsten 89–93

two-electron dioxygen reduction 114

596 INDEX

urea 247, 248, 252, 253, 263, 264, 276

urethanes 266, 268

valence band 274

vanadium 83

vanadium carbonyls 475–478

vanadium complexes 355–356, 358, 360,

362, 371, 382

Vaska’s complex 132, 135

vibrational spectroscopy 190, 191, 193,

195, 201–203, 205, 209–226,

232–236

volume of activation 345, 347, 351–356,

360–370, 375, 383

volume of reaction 370

volume, partial molar 353–354, 362–363,

368–369

Walsh diagram (of CO2) 248, 249, 276

water exchange 354–366

water splitting 272

water-soluble complexes 255, 256

Wheland intermediate 528–529

X-ray diffraction 201

zeolite binding of H2 200, 223, 226, 229

zero point energy term in isotope

effect 232–234

zinc(II) complexes 352, 355, 357, 362, 382

INDEX 597