aacetaldehyde 249acid 261– acetic 238, 274– acretic 339activation barrier 266aerobic oxidation 159, 170, 175air 242Alberto’s reagent 301alcohol oxidation 163aldehydes 161, 164alkane 238– complex 246, 258alkyl boranes 278alternative fuels 121amine ligands 177ammonia 238antiferromagnetic coupling 220, 227aqueous solvents 249artificial processes 12atom-efficiency 241

bB(C6F5)3 261Baeyer-Villinger 278 ffbasicity leveling 261benzene 265Bergman 260bimetallic molybdenum systems 93BINAS 331biomimetic systems 86bipyrimidine 255bis(p-nitrophenyl)phosphate 304BISBI 330bite angle 330Bond Metathesis 247 ffBronsted acids 259fBrookhaven catalyst 321

ccalculations 262, 277, 281calix[4]arenes 3272�,3�-cAMP 308carbamates 10, 17carbon sources 1carbonates 10, 20, 26– linear 22 ffcarbon dioxide (CO2) 1 ff, 235, 274– C-C bond formation 10– C-O bond length 7– conversion 5, 9– coordination to metal centers 6– electronically excited 3– emission 2– gaseous 3– interaction with metal atoms 8– molecular geometry 3– properties 3– radical anion 3– reactivity 8– solid 3– utilization 2, 11carbon monoxide (CO) 319– heterogeneous processes 319– homogeneous catalysts 32113CO labeling 336carbonic anhydrase II 289, 292, 294– pKa 288carbonyl complexes, acidity 301carbonylation catalysis 319carboxylase 11carboxylation 10 f– enzymes 12– of alcohols 22– of alkenes 13– of alkynes 14– of epoxides 18– of methane 13– reactions 10

357

Activation of Small Molecules. Edited by William B. TolmanCopyright © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimISBN: 3-527-31312-5

Subject Index

carboxylic acid 10, 273carboxypeptidase A 289, 292– pKa 288catalyst 247, 257, 259– de novo 245– heterogeneous 20– homogeneous 20– metal 243– oxidation 240ff– stable 243catalytic hydrolysis 287catalytic NO reduction 54CATIVA 339, 349– mechanism 350C-C bond formation 8, 10CH activation 245ff, 253, 276, 278, 282– heterolytic 267CH cleavage 246, 258CH bonds, aromatic 268CH4 10, 250Chatt cycle 87 f, 116Chatt systems 107chelation 257chemical bonding– computational studies of hydrogen

activation 127f– Dewar-Chatt-Duncanson (DCD) model

H2 binding 125, 127– frontier molecular orbital

theory 122ffchemoselective oxidation 160chloroperoxidase (CPO) 208chromate 187cluster models 10413C nuclear magnetic resonance (NMR) 4cobalt complexes– Co(I)Tp complexes 222– Co(III) aqua complexes 296– Co(III)-peroxo complex 222– pKa 299cobalt-dioxygen complexes 220cocatalysis– copper 166, 168– metal 166– organic 166cofactor 11commodity 239coordination 245coordination number 288, 298, 313coordination sphere 190f, 191copolymerization 20copper 298, 306– Cu(II) aqua complex 296

– Cu(II)-superoxide 206– Cu(III)(�-O)2Cu(III) motifs 215– Cu(III)-peroxide 206– Cu-NIR 61– Cu-O vibration 216– Cu-O2 adducts 206copper nitrite reductase (Cu-NIR) 51– computational studies 51– synthetic model 51– X-ray structures 51copper-dioxygen complexes 204copper-dioxygen species 204copper-nitrosyl complex 51, 65coupled catalytic systems 165cyclic carbonates 18cytochrome P450 171, 188

dd0 metal 282denitrification 72density functional theory (DFT) 93DFT methods 96DFT studies 97dicopper complexes 203dicopper (II)-peroxo complex 202dihydrogen, see H2

dihydroxylation 179diiron complexes 197diiron(II) complex 219diiron N2 reduction scheme 103diiron sites 99 ffdiiron system 196diiron-peroxo complexes 197dinitrosyl species 62, 65dinuclear catalysts 347dioxygen 187, 214– activation 187– binders 192– binding 187, 198– cleavage 211– reactive intermediates 187diphosphites 326double-stranded DNA 201DPEphos 333

eelectricity 236electrocatalytic reduction cycle 89electron-nuclear double resonance

(ENDOR) 84felectrophiles 251electrophilic catalytic system 267

Subject Index358

Electrophilic Substitution (ES) 247ff,251

– pathway 250endothelial-derived relaxing factor 44Enemark-Feltham notation 45energy production 235epoxidation 161 f– aerobic olefin 162– asymmetric 162– of olefin 21– stereoselective 162ESCH Activation 271ethanol 250ethylene 242, 249

fFe(0)-N2 complexes 108Fe(II) precursors 214Fe(III) aqua complex, pKa value 301Fe(IV)= O complexes 213, 214Fe(�-O)2Fe motifs 218FeFe 83FeMo cofactor 84FeMo nitrogenase 86Fe-N2 intermediate 107Fe-N2 reduction cycle 111Fe-N-Fe bridges 105[BP3]Fe iron systems 116ferric-peroxo complexes 201Fischer-Tropsch reaction 320free radical 240, 248functionalization 237, 239– of methane 238

ggas-liquid bubble column reactors 243gas-to-liquid (GTL) 31, 319, 320green oxidant 187ground state 261ground state inhibition 259ground state stabilization 257, 259guanyl cyclase 47– soluble (sGC) 48

hH2 121ff– binding to transition metal 124f– concerted addition to ethylene 123H2SeO4 272H-bond acceptor 126, 296H-bond donors 126fH-bonding 288 ff, 293 ff, 298, 302, 312 f– anion coordination 303

– M-OH2 288, 298– phosphate ester 298, 306– pKa 314, 288– transition state stabilization 308– zinc hydroxide stabilization 297H-bonds, non classical 136fheme-NO complex 60, 62– nitrosyl porphyrinate complexes 47heme-NO interactions 47hemerythrin 193, 196f, 201hemocyanin 194, 202hemoglobins 192heterolytic CH activation 267hexaaqua ion 314– acidity 301Hg(II)/H2SO4 251H-H bond– dissociation energy 122– experimental measurement 129– frontier molecular orbitals 122–123– 1H NMR Studies 130– heterogeneous activation by extended

systems 121– heterolytic cleavage 122ff, 139 ff– H-H distance 126, 128ff– homolytic cleavage 122, 126 f– inelastic neutron scattering (INS) 133f– infrared Spectroscopy 130– neutron diffraction 129– Raman Spectroscopy 130f�2-H2 complexes 125f– �2-H2/hydride exchange 134f– stability 127 f– transient formation of 135– types 128high-pressure IR 334hybrid tetradentate ligands 292hydration 250hydride-hydride exchange 135�-hydride elimination 278hydrocarbons 235hydroformylation 322– 2-alkenes 335– alkylphosphines as ligands 337– arylphosphines as ligands 328– bimetallic catalysts 338– incubation 328– kinetics 324, 328– mechanistic studies 336– Mitsubishi Chemical Corporation 322– of 1-octene 334– of styrene 334– phosphites as ligands 324

Subject Index 359

– rhodium carbonyls 323– rhodium catalysts 322– Ruhrchemie/Rhône-Poulenc pro-

cess 322– Union Carbide Corporation (UCC) 322hydrogen 248hydrogen peroxides 239hydrogenase 143ff– iron-iron 145ff– nickel-iron 143ffhydrogenations 245hydroperoxo ligand 207hydrophobic effect 289hydroxo complex 269hydroxylation 238hyponitrite 62, 65

iimido-bridge-cluster 106industrially important reactions 121inhibition 257, 264inner sphere 245intermolecular H-atom exchange 131– hydride-hydride exchange 135– rotation of �2H2 ligands 132iodosyl benzene 278IR spectroscopy 342– high pressure 334iridium 349iron center 190 firon model systems 109iron N2 adduct synthesis 112iron-dioxygen complexes 200iron-sulfur cluster 105isonitrosyl 50isotopic shift 216

k�2-N, O-picolinate (pic) 265

llactones 10Lewis acidity 260, 288 f, 313ligand motifs 253linear carbonates 22– DFT calculations 24– heterogeneous catalysts 24– homogeneous catalysts 24– methyl-phenyl-carbonate 24– reactions mechanism 24linkage isomerism 52liver alcohol dehydrogenase 302LUMO 251

mM(�-O)2M motifs 215manganese-dioxygen complexes 224maximum yield 243metal catalyst 161metal hydrides 278metal hydroxide 287metal nitrosyl chemistry 52metal nitrosyl compounds 53– coordination geometry 46– infrared (IR) spectroscopy 53– isonitrosyl 50– linkage isomers 50– NO reductive lavage 57– nuclear magnetic resonance (NMR) 53– O-atom transfer 54– side-one �2-NO complexes 50metal-bound H-atoms– reactivity 137– compared to free H2 137f– increases acidity 139 fmetal-dioxygen adducts 207metal-iron-sulfur cluster 106metalloproteins 190metalloradical,1,2 addition 253metal-nitrosyl chemistry 52metal-nitrosyl compounds 45methane 10, 235 ff, 263– solubility 241methane monooxygenase (MMO) 191methanol 237 ff, 263– carbonylation 339– catalyst development 32– dehydrogenase 33– from CO2 and water 33– homogeneous processes 321– miscibility 241– production 2, 32MMOH 218Mn(III)TPP(O2) complex 226MoFe nitrogenase 82M-OH2 288, 298molecular mechanics 332molecular oxygen 159ffMo-N2 complexes 95mononuclear molybdenum systems 86mono-hydride complexes 138Monsanto process 340– ligand design 344– mechanism 340– rate-limiting Step 342Mössbauer parameters 197, 199Mössbauer spectroscopies 212

Subject Index360

MTO 279multiple-iron-site 96

nNa/Hg reducing complex 111NAPHOS 331natural bite angle 330natural gas 236natural processes 11N-C bond formation 17nickel-dioxygen complexes 227nitric oxide see nitrogen monoxidenitride-bridged cluster 106nitrile hydratase, pKa 299nitrogen (N2)– adducts 102– – of iron 98– donors 110– fixation 81ff, 107– fixation cycle 108– – intermediates 92– reduction 82, 87, 96– – biological 61, 83– – metal-bound 53– – Mo(III)-mediated 90nitrogen monoxide (NO) 43, 49– atmospheric chemistry 43– binding 47– biological roles 43– bridging 49 f– catalytic reduction 53– copper protein 51– coupling of two NOs to N2O 62– disproportionation 65– Lewis structure 44– molecular orbital (MO) diagram 45– sensing 44– synthase 48NO reductases (NORs) 61– active site 61– bacterial 61– binuclear center 61– flavorubredoxins 64– fungal P450-type 63– models 63– nonheme diiron center 64– scavenging (S)-NORs 64– single heme center 63NO reduction 59 f– catalytic 54– biological 61– electrocatalytic 60nitrogen/sulfur(thiolate) ligands 293

nitrogenase 83, 148 f– cofactor 95– FeFe 83– Mo-containing 83, 149– MoFe 83– VFe 83nitrogenase-related transformation 104nitrogen-fixing catalysts 82nitrosonium cation 45nitrous oxide (N2O) 43, 242– activation 68 see also N2O reduction– – nitride complexes 70– – nitrosyl complexes 70– – N-N bond cleavage 70– binding modes 67– bonding 66– coordination complex 67– greenhouse gas 43– Lewis structure 66– ozone layer depletion 43– reductase– – Cu4S cluster 71, 72– – CuZ catalytic center 71– – pathway for N2O reduction 71N2O reduction 68, 71– biological 72– catalytic oxo transfer 70– electrocatalytic 71– heterogeneous catalysis 70– N2O insertion 68– oxo transfer reactions 68nitroxyl anion 45nitroxyl complexes 58– chemistry 58– generation, synthetic routes 59– heme-HNO complex 60N3O-donor ligands 294fnon-free radical 277nonheme– Fe(IV)-oxo species 212– iron center 61– iron enzyme 210– iron systems 209– Mn(III)-peroxo complexes 226

oO2 reduction 107O-Atom 278O-C bond formation18O-donor 257olefin 249– oxidative carboxylation 20O-O bond length 222

Subject Index 361

O-O vibration 194organometallic reactions 245organometallic aqua ions 287, 300 f, 314– acidity 300– water exchange properties 300oxidant 253oxidase system 159oxidation– aerobic alcohol 176– catalysis 159– chemoselective 180– homogeneous aerobic 159– O2 coupled 177– palladium catalyzed 176, 178oxidative addition (OA) 247ff., 264, 342– mechanism 342oxidative decarbonylation 163oxidative insertion 273oxovanadium 175oxyfunctionalized products 276oxygen 242oxygenase systems 159oxyhemocyanin 202fozone 242

pP450 280P450NOR 64palladium 249pentamethylcyclopentadienyl ligand 300peptide deformylase 289, 293– pKa 288permanganate 187peroxocarbonate formation 21�-peroxo diiron complexes 198persulfates 242petrochemical industry 282petroleum 236phosphate 324phosphate diester 298, 302 f– H-bonding 298phosphate ester 298, 302 f, 308 ff– cleavage 306– coordination 302– hydrolysis 314phosphines 180phosphonites 327phosphoramidites 327photocatalysts 34photo-electro-chemical reduction 33pKa 299

– ligand effects 299polymerization 245

polymetallic iron mechanisms 104polyoxometalates (POM) 180polypyridine ligands 213porphyrin catalysis 171porphyrin ligand 195pressure 241protons 248proton dissociation constant 124, 138Pt black 265Pt(II) 255pyridine 269

rradiopharmaceutical imaging 287, 301,

314– organometallic aqua ion 301Raman studies, resonance 198rate 244, 252, 263redox couples 165reductant 239reduction reactions 28– artificial processes 29– biomimetic systems 29– natural processes 28– syngas production 30reductive eliminations 270reductive protonation 92reoxidation rate 165rhodium carbonyls 323RNR 218RuBisco 11Ruhrchemie/Rhône-Poulenc process 331

sSchiff bases 172, 174Schrock system 91, 93, 107Schulz-Flory distribution 320selectivity 243fselenic acid 272Shell Middle Distillation Synthesis

(SMDS) 320Shilov 254shunt pathway 115Sigma Bond Metathesis 254single iron sites 96, 107fsingle-site molybdenum 96six-membered transition state 266solubility of methane 241sources of carbon 1SPANphos 343, 348stability 244steric congestion 298sulfide-bridge iron complex 110

Subject Index362

sulfuric acid 251f, 271superoxo ligand 204fsyngas 30, 237, 319synthetic dicopper system 202synthetic iron complex 195

ttaurine dioxygenase (TauD) 209technetium 15technological fluid 1ftechnologies 236tetradentate N4-donor chelate ligands 291thiolate-alkylating enzyme 302tmc ligand 212trans-diphosphines 347transesterification reactions 27transition metal complex 188transition state stabilization 310tridentate N3-donor chelate ligands 290turnover frequency (TOF) 165turnover number (TON) 165

uUCC/Johnson Matthey process 328urea 2, 26urethanes 26

wWacker system 242, 249Wacker-type oxidations 169– applications 168water 253, 263water activation 287– primary coordination environment 288water-gas-shift reaction 32

xXantphos 332, 344X-ray absorption spectroscopy (XAS) 208XRD measurements 218XRD methods 207, 212, 226XRD studies 205, 222

yYOs 280

zzinc 288 ff, 306f, 310 ff– alkoxide 312– hydrolytic enzymes 288– hydroxide 297, 309

Subject Index 363