Sdarticle 011

INDEX
Actinides divalent state 19

solvent exchange reactions 3, 49^52 e¡ect of non-leaving ligands 33
aqua ions 51 trivalent state 25
Aldehydes, tris(imido)rhenium(VII) Cobalt
reactions 198 catalysis of autoxidation 419
Aluminum ligand substitution reactions in
reactions at labile Al(III) centers 122 octahedral Co(III) complexes
solvent exchange data 12, 16 aquation and related reactions
Anthraphos rhodium complex 342^343 75^78
L -ascorbic acid base hydrolysis 80^81
autoxidation 400^411 biochemical models and systems
non-linear autoxidation behavior 449^452 78^80
Associative ligand substitution reactions kinetic parameters for base hydrolysis
(A-mechanism) 5, 8, 18 81
Autoxidation catalyzed by metal ions rate constants for aquation and base
395^396 hydrolysis 76
autoxidation of L -ascorbic acid 400^411 reactions at labile Co(II) centers 111
autoxidation of catechols and related solvent exchange data
compounds 411^426 divalent state 20
autoxidation of cysteine 426^431 e¡ect of non-leaving ligands 31
anaerobic oxidation with hydrogen Copper
peroxide 427 divalent ¢ve-coordinate structures 23
autoxidation of miscellaneous substrates non-linear autoxidation of L-ascorbic acid
442^448 449^452
exotic kinetic phenomena 449^454 outer-sphere electron transfer reactions
general considerations 397^400 at mixed-valent [Cu2]3+ centers
354^356
Benzaldehyde, non-linear autoxidation reactions at labile Cu(II) centers
behavior 452^454 dissociation and ligand replacement
Beryllium, solvent exchange data 10 114^115
Bismuth, reactions at labile Bi(III) centers ¢ve-coordinate centers 115^116
123 formation reactions 112^114
solvent exchange data
Cadmium, reactions at labile Cd(II) centers divalent state 21
117^118 e¡ect of non-leaving ligands 31^32
Carbon monoxide, activation energies for Cyanide complexes, high oxidation state
ligand exchange 109 complexes 95^96
Catalytica system 261, 300 Cysteine
Catechols, autoxidation 411^426 autoxidation 426^431
Catenanes 137 anaerobic oxidation with hydrogen
Chromium peroxide 427
ligand substitution reactions in Cytochrome c oxidase, electron-transfer
octahedral Cr(III) complexes reactions 372^374
81^83 Cytochrome P450, electron-transfer
solvent exchange data reactions 378^379
463
464 INDEX
Density functional studies of iridium- internal electron transfer in sul¢te

catalyzed dehydrogenation 321^323, oxidase 374^376
343^344 ‘‘wired’’cytochrome P450 378^379
acceptorless reaction 337^338 outer-sphere electron transfer reactions
associative mechanism (A) 338 computation of self-exchange rate
dissociative mechanism (D) 339 constants 356^358
interchange mechanism (I) 339^340 dual-pathway square scheme 361
anthraphos rhodium complex 342^343 electron transfer coupled to change in
computational details 344^345 ligand number 359^361
cyclopentadienyl iridium complex 323^324 ion-pairing inhibition of electron-
basis set impact 326^328 transfer kinetics 358^359
ligand replacement 328^329 mixed-valent [Cu2]3+ centers
study methodology 324^325 354^356
thermodynamic data 327 PAF studies of very rapid electron
fundamental steps 329^336 transfer 352^353
intermediates 330 radical electron-transfer reactions
thermodynamic data 331, 332, 333 361^362
geometric factor 340 electron-transfer reactions of phenoxy
model with tert-butyl phosphine 342 radicals 368^369
.
reaction conditions 340^341 generation of SO3 in the oxidation of
free energy pro¢les 341 S(IV) by Fe(III) 364^366
transfer reaction 336^337 one-electron pathways for aqueous
free energy pro¢le 337 chlorine reduction 363^364
thermodynamic data 336 outer-sphere oxidation of thiols
4,6 -Dimethyldibenzothiophene 183 366^368
. .
Dissociative ligand substitution reactions oxidation of Br2 by ClO2 362^363
(D-mechanism) 5, 8, 18, 28^29 small molecule intramolecular electron-
Dysprosium, solvent exchange data transfer reactions
aqua ions 42 picosecond events in intramolecular
DMF exchange 48 molecular transfer 369^370
TMU exchange 48 structural models of inner-sphere
electron-transfer transition states
Electron-transfer reactions 352 370^372
double electron transfer Erbium, solvent exchange data
Tl3+/Tl+ self-exchange reactions aqua ions 42
379^381 DMF exchange 48
electrochemical electron-transfer TMU exchange 48
reactions Europium, solvent exchange data
activation parameters for coupled aqua ions 42
electron transfer and spin exchange divalent Eu(II) complexes 47^49
383^385 e¡ect of non-leaving ligand 45
metalloprotein ¢lm voltammetry
390^392 Flavonols, autoxidation 442^443
outer-sphere oxidation of ClO2
381^383 Gadolinium, solvent exchange data
photoelectrochemical cells 385^389 aqua ions 42
electron transfer with metalloproteins e¡ect of non-leaving ligand 45
cytochrome c oxidase 372^374 Gallium
electron-transfer kinetics of blue reactions at labile Ga(III) centers 122
copper proteins 376^377 solvent exchange data 12
INDEX 465
Gold oxidation by sulfur trioxide and redox

ligand substitution reactions in square- mediators 301^303
planar Au(III) complexes 108 oxidation of Pt(II) by dioxygen
solvent exchange data 303^306
square-planar complexes 38 oxidative addition versus electron
transfer 299^301
Helicates 137^139
Heme Incoherent quasi-elastic neutron scattering
activation of heme-containing enzymes (IQENS), determination of solvent
238^243 exchange rate constants 4^5, 8
reactions with nitric oxide 210^212 Indium
rate constants 210 reactions at labile In(III) centers 122
S-Hemoglobin, nitrosylated (SNO-Hb) solvent exchange data 13
243^245 Interchange ligand substitution reactions
Holmium, solvent exchange data (I-mechanism) 5, 8, 18
aqua ions 42 Intimate mechanisms of ligand substitution
DMF exchange 48 reactions (Ia- and Id-mechanisms)
TMU exchange 48 5^6, 7^8, 18, 28^29
Horseradish peroxidase (HRP) 242, 449 Iridium
Hydrocarbon C^H bond activation and ligand substitution reactions in
functionalization with platinum octahedral Ir(III) complexes 83^84
260^263, 311^313 ligand substitution reactions in square-
classical division of functionalization planar Ir(I) complexes 108^109
cycle 263^264 solvent exchange data 27
functionalization sequence mechanisms e¡ect of non-leaving ligands 36
306^307 Iridium-catalyzed dehydrogenation,
alkane dehydrogenation 310^311 density functional studies 321^323,
carbon heteroatom coupling reactions 343^344
from Pt(IV) 307^309 acceptorless reaction 337^338
mechanisms for C^H activation 264 associative mechanism (A) 338
activation of R^H by Pt(II) complexes dissociative mechanism (D) 339
possessing a labile ligand 266^268 interchange mechanism (I) 339^340
associative or dissociative substitution anthraphos rhodium complex 342^343
291^295 computational details 344^345
computational approach to ¢ve- cyclopentadienyl iridium complex
coordinate intermediates and 323^324
-complexes 283^288 basis set impact 326^328
computational approach to the ligand replacement 328^329
electrophilic pathway 288^291 study methodology 324^325
degree of electrophilic nature of Pt(II) thermodynamic data 327
complexes 295^299 fundamental steps 329^336
direct oxidative addition of R^H to intermediates 330
square-planar Pt(II) 264^266 thermodynamic data 331, 332, 333
¢ve-coordinate Pt(IV) intermediates geometric factor 340
and Pt(II) -complexes 263^278 model with tert-butyl phosphine 342
stable ¢ve-coordinate Pt(IV) complexes reaction conditions 340^341
278^282 free energy pro¢les 341
stable -complexes and related species transfer reaction 336^337
282^283 free energy pro¢le 337
oxidation step mechanisms thermodynamic data 336
466 INDEX
Iron binary and ternary cyanide complexes

catalysis of oxidative removal of hydrogen 95^96
sul¢de 448 platinum(IV) 94
iron(III) catalyzed autoxidation of vanadium(IV) and vanadium(V) 95
sulfur(IV) 432 inert octahedral complexes
ligand substitution reactions in chromium(III) 81^83
octahedral Fe(II) low-spin complexes cobalt(III) 75^81
complexes of macrocyclic ligands 86 iridium(III) 83^84
diimine complexes 85^86 iron(II) low-spin complexes 84^89
diphosphine complexes 86 osmium 94
pentacyanoferrates(II) 87^89 rhodium(III) 83^84
spin cross-over 84^85 ruthenium(II) 89^91
porphyrin systems 212^219 ruthenium(III) 91^93
reactions at labile Fe(II) centers 110^111 reactions at labile metal centers 109^110
reactions at labile Fe(III) centers 119^122 aluminum(III) 122
solvent exchange data bismuth(III) 123
divalent state 20 cadmium(II) 117^118
e¡ect of non-leaving ligands 33^34 cobalt(II) 111
trivalent state 25 copper(II) 112^116
Isotopic labeling, determination of solvent gallium(III) 122
exchange rate constants 4 indium(III) 122
iron(II) 110^111
Knots 139 iron(III) 119^122
lanthanides(III) 123^126
Lanthanides mercury(II) 117^118
reactions at labile M(III) centers 123 nickel(II) 111^112
complex formation 123^124 nickel(III) 123
complex^substrate interaction 124^125 rhodium(II) 116^117
dissociation of macrocyclic complexes sp-block elements 118
125^126 zinc(II) 117^118
polynuclear cation formation 126 square-planar complexes 96^97
solvent exchange reactions 3 gold(III) 108
absolute partial molar volumes 43 iridium(I) 108^109
divalent Eu(II) 47^49 kinetic parameters for cyanide
DMF exchange 48 exchange 97
TMU exchange 48 nickel(II) 107^108
trivalent metals 41^47 paladium(II) 105^107
water exchange mechanisms 44 platinum(II) 97^105
Ligand ¢eld activation energy (LFAE) rhodium(I) 108^109
16^17 triangles and clusters 126^128
Ligand substitution reactions 72^75 Luminol, oxidation 447
coordinated ligands Lutetium, solvent exchange data
metal-catalyzed hydrolysis of organic TMU exchange 48
compounds 129^133
nucleophilic attack 128^129 Magnesium, solvent exchange data 11
rotaxanes, catenanes and knots Manganese
136^139 catalysis in autoxidation of sulfur(IV)
supramolecular chemistry 133^136 438^441
template reactions 133 solvent exchange data
high oxidation state complexes divalent state 19
INDEX 467
e¡ect of non-leaving ligands 31 chemical biology examples 237^238

Mercury, reactions at labile Hg(II) centers activation of heme-containing enzymes
117^118 238^243
Metal catalyzed hydrolysis of organic S-nitrosylated hemoglobin (SNO-Hb)
compounds 129^130 243^245
carboxylate esters 131 formation of metal nitrosyl complexes 206
other substrates 131^133 heme reaction kinetics 210^212
phosphate esters 130^131 iron porphyrin studies 212^219
Metal ion catalyzed autoxidation reactions metalloporphyrins 208^209
395^396 ruthenium ammine complexes 207
autoxidation of L -ascorbic acid 400^411 ruthenium(III) salen complexes
autoxidation of catechols and related 207^208
compounds 411^426 metal^nitrosyl complexes 219
autoxidation of cysteine 426^431 disproportionation of NO 229^233
anaerobic oxidation with hydrogen electron transfer reactions 220^222
peroxide 427 electrophilic reactions 228^229
autoxidation of miscellaneous substrates nucleophilic reactions 222^225
442^448 reactions with dioxygen 233^237
autoxidation of sulfur(IV) 431^441 reductive nitrosylation reactions
exotic kinetic phenomena 449^454 225^227
general considerations 397^400 Nitrosonium cation 205
perspectives 455^457 S-Nitrosylated hemoglobin (SNO-Hb)
Metalloporphyrins 208^209 243^245
mechanism studies with iron systems Nitroxyl anion 205^206
212^219 Non-linear behavior in autoxidation
Metalloproteins reactions 449^454
blue copper proteins 376^377 Nuclear magnetic resonance (NMR)
cytochrome c oxidase 372^374 spectrometry, determination of
cytochrome P450 oxidase 378^379 solvent exchange rate constants 3^4
metalloprotein ¢lm voltammetry 390^392
trumpet plots 391 Organic compounds, metal-catalyzed
sul¢te oxidase 374^376 hydrolysis 129^130
4-Methylpyridine N-oxide 164 carboxylate esters 131
Molybdenum, catalysis by 163^164 other substrates 131^133
Myeloperoxidase (MPO) 241^242 phosphate esters 130^131
Osmium
Neptunium, solvent exchange data ligand substitution reactions in
aqua ions 51 octahedral complexes 94
Nickel solvent exchange data
ligand substitution reactions in square- e¡ect of non-leaving ligands 35
planar Ni(II) complexes 107^108 Oxidative stress 233
reactions at labile Ni(II) centers 111^112 Oxygen activation 190
reactions at labile Ni(III) centers 123 phosphine autoxidation
solvent exchange data dissociation and substitution 193^194
divalent state 20^21 rate constants 195
e¡ect of non-leaving ligands 31 reactions with oxygen 194^195
square-planar complexes 38 phosphine oxidation
Nitric oxide, reaction mechanisms with kinetics 191^192
biologically relevant metal centers rhenium-phosphine coordination 191
203^206, 245^248 {ReO}2(mtp)3 catalysis 192
468 INDEX
Oxidative activation (Cont.) reaction scheme 167^168

competition experiments 193 reaction between 4 -methylpyridine
kinetics 193 N-oxide and triphenylphosphine
{ReO}2(mtp)3 substrates 192 catalyst structure-activity correlations
Oxygen transfer reactions, catalysis by 164
rhenium compounds 158 thermochemical considerations 164^165
catalyst attributes
electronic structure 159 Palladium
oxophilicity 162^163 ligand substitution reactions in square-
oxorhenium compounds 163 planar Pd(II) complexes 105^107
steric considerations 158^159 solvent exchange data
structural data 159 square-planar complexes 37, 40
structural motif 161^162 Pentacyanoferrates(II), formation and
4,6 -dimethyldibenzothiophene 183 dissociation parameters 87
ligand exchange and substitution 173 Photoelectrochemical cells 385^386
microscopic reversibility 173^174 electron transfer with tripodal dyes
monomerization of dimeric bound to TiO2 388^389
oxorhenium(V) compounds 177^179 electron-transfer dynamics in TiO2/
phosphine exchange and substitution sensitizer systems 386^388
175^177 Pincer complexes 322
pyridine exchange reactions of Platinum, homogeneous hydrocarbon C^H
MeReO(edt)Py 174^175 bond activation and
rate constants 178 functionalization 260^263, 311^313
turnstile mechanism 177 classical division of functionalization
oxorhenium(V) compounds with cycle 263^264
tridentate ligands 186 functionalization sequence mechanisms
OSO tridentate ligand 186 306^307
SOS tridentate ligand 186 alkane dehydrogenation 310^311
oxygen transfer from tert-butyl carbon heteroatom coupling reactions
hydroperoxides to sul¢des 180 from Pt(IV) 307^309
catalytic cycle 182 mechanisms for C^H activation 264
kinetics of sulfoxide formation 180^181 activation of R^H by Pt(II) complexes
reaction scheme and mechanism possessing a labile ligand 266^268
181^182 associative or dissociative substitution
oxygen transfer from tert-butyl 291^295
hydroperoxides to sulfoxides computational approach to ¢ve-
sulfone-forming reactions 182 coordinate intermediates and
thianthrene, oxidation of 183 -complexes 283^288
PAr3 oxidation by a rhenium(V) dimer computational approach to the
184^185 electrophilic pathway 288^291
phosphine oxidation by tert-butyl degree of electrophilic nature of Pt(II)
hydroperoxide 183^184 complexes 295^299
pyridine N-oxide, reduction of 165 direct oxidative addition of R^H to
initial step 168 square-planar Pt(II) 264^266
nucleophilic assistance 169^170 ¢ve-coordinate Pt(IV) intermediates
PR3 stage mechanism 172^173 and Pt(II) -complexes 263^278
putative role of Rh(VII) 170^172 stable ¢ve-coordinate Pt(IV) complexes
pyridine liberation 169 278^282
rate law 166^167 stable -complexes and related species
reaction partners 165^166 282^283
INDEX 469
oxidation step mechanisms kinetic competition 170

oxidation by sulfur trioxide and redox synthetic analogues of
mediators 301^303 dioxorhenium(VII) dithiolates
oxidation of Pt(II) by dioxygen 303^306 171^172
oxidative addition versus electron pyridine liberation 169
transfer 299^301 rate law 166^167
Platinum reaction partners 165^166
¢ve-coordinate Pt(IV) intermediates reaction scheme 167^168
methyl(hydrido)platinum(IV)
complexes 270^276 Rhenium
Pt(IV) alkyl halides 276^278 rheniumôxygen bond distances 160^161
reductive elimination in hydrocarbons solvent exchange data 27
to give C^C bonds 268^270 Rhenium catalysis of oxygen transfer
reductive elimination in hydrocarbons reactions 158, 200
to give C^H bonds 270^278 catalyst attributes
high oxidation state complexes, Pt(IV) 94 electronic structure 159
ligand substitution reactions in square- oxophilicity 162^163
planar Pt(II) complexes oxorhenium compounds 163
dissociative substitution 102^105 steric considerations 158^159
intramolecular processes 105 structural data 159
ring closing and ring opening 99^100 structural motif 161^162
substitution 97^99 4,6 -dimethyldibenzothiophene 183
systems of biochemical and imido-rhenium compounds
pharmacological revelance 101^102 hydrolysis, hydrosul¢dolysis and
Pt(II) -complexes aminolysis 199^200
dihydrogen complexes 282 pairwise oxo-imido exchange reactions
electrophilic nature 295^299 196^197
oxidation by dioxygen 303^306 tris(imido)rhenium(VII) compounds
oxidative addition cleaving C^H bonds 196
in hydrocarbons 270^278 tris(imido)rhenium(VII) reactions with
Z2 -benzene complexes 282^283 aldehydes 198
solvent exchange data ligand exchange and substitution 173
square-planar complexes 37^38, 40 microscopic reversibility 173^174
stable ¢ve-coordinate Pt(IV) complexes monomerization of dimeric
278^282 oxorhenium(V) compounds 177^179
Plutonium, solvent exchange data phosphine exchange and substitution
aqua ions 51 175^177
Pseudorotaxanes 136 pyridine exchange reactions of
Pulsed-accelerated-£ow (PAF) method 352, MeReO(edt)Py 174^175
353 rate constants 178
schematic of apparatus 354 turnstile mechanism 177
Pyridine e¡ect 188^189 oxorhenium(V) compounds with
Pyridine N-oxide, reduction by rhenium tridentate ligands 186
compounds 165 OSO tridentate ligand 186
initial step 168 SOS tridentate ligand 186
nucleophilic assistance 169^170 oxygen transfer from tert-butyl
PR3 stage mechanism 172^173 hydroperoxides to sul¢des 180
putative role of Rh(VII) 170 catalytic cycle 182
detection by low-temperature NMR kinetics of sulfoxide formation
spectroscopy 171 180^181
470 INDEX
Rhenium catalysis of oxygen transfer ligand substitution reactions in square-

reactions (Cont.) planar Rh(I) complexes 108^109
reaction scheme and mechanism reactions at labile Rh(II) centers 116^117
181^182 solvent exchange data 27
oxygen transfer from tert-butyl e¡ect of non-leaving ligands 36
hydroperoxides to sulfoxides Rotaxanes 136
sulfone-forming reactions 182 Ruthenium
thianthrene, oxidation of 183 catalysis of autoxidation 444^447
PAr3 oxidation by a rhenium(V) dimer ligand substitution reactions in
184^185 octahedral complexes
phosphine oxidation by tert-butyl Ru(II) 89^91
hydroperoxide 183^184 Ru(III) 91^93
putative role of Rh(VII) 170 ruthenium(III)^salen complexes 207^208
detection by low-temperature NMR rutheniumâmmine complexes 207
spectroscopy 171 solvent exchange data 27
kinetic competition 170 e¡ect of non-leaving ligands 35, 36
synthetic analogues of
dioxorhenium(VII) dithiolates Scandium, solvent exchange data 13
171^172 TMU exchange 48
pyridine N-oxide, reduction of 165 trivalent state 25
initial step 168 Shilov cycle 261, 299^300
nucleophilic assistance 169^170 Sitting-atop (SAT) complexes 114
PR3 stage mechanism 172^173 Solvent exchange reactions on metal ions
putative role of Rh(VII) 170^172 1^3
pyridine liberation 169 classi¢cation of reactions 5^6
rate law 166^167 experimental methods 3^5
reaction partners 165^166 main group metals 8
reaction scheme 167^168 divalent ions 9^11
reaction between 4 -methylpyridine e¡ect of non-leaving ligands on solvent
N-oxide and triphenylphosphine exchange rate constants 16
catalyst structureâctivity trivalent ions 11^16
correlations 164 volume of activation 6^8
thermochemical considerations Sul¢te oxidase, electron-transfer reactions
164^165 374^376
Rhenium catalysis of sulfur atom postulated oxidation state changes 375
abstraction reactions Sulfoxide disproportionation 190
abstraction from thiranes 189^190 Sulfur
imidorhenium m-S compounds autoxidation of sulfur(IV) 431^441
.
reactions with phosphines 187^188 generation of SO3 in the oxidation of
structures 187 S(IV) by Fe(III) 364^366
oxygen atom transfer between sulfoxides typical kinetic traces 365
190 Sulfur atom abstraction reactions
oxygen atom transfer from sulfoxide to abstraction from thiranes 189^190
sul¢de 189^190 imidorhenium m-S compounds
Rhodium reactions with phosphines 187^188
anthraphos complex 342^343 structures 187
ligand substitution reactions in oxygen atom transfer between sulfoxides
octahedral Rh(III) complexes 83^84 190
kinetic parameters for water oxygen atom transfer from sulfoxide to
replacement 83 sul¢de 189^190
INDEX 471
Template reactions 133 Turnstile mechanism for ligand

Terbium, solvent exchange data substitution 177
aqua ions 42
DMF exchange 48 Uranium, solvent exchange data
TMU exchange 48 aqua ions 51
Thallium
solvent exchange data Vanadium
aqua ions 42 high oxidation state complexes,V(IV) and
DMF exchange 48 V(V) 95
TMU exchange 48 solvent exchange data
Tl3+/Tl+ self-exchange reactions 379^381 divalent state 19
Thianthrene, oxidation of 183 oxo-ions 30
Thorium, solvent exchange data trivalent state 25
aqua ions 51 V|tamin B12 220
Titanium, solvent exchange data
oxo-ions 30 Water, mean liftimes for metal ion
trivalent state 25 coordination 2
Transition metals
solvent exchange reactions 3, 16^17 Ytterbium, solvent exchange data
divalent ¢rst-row metals 18^24 aqua ions 42
e¡ect of non-leaving ligands 29^32 DMF exchange 48
¢rst-row oxometal ions 30 TMU exchange 48
second and third-row octahedral Yttrium, solvent exchange data
complexes 26^29 TMU exchange 48
square-planar complexes 32^39
trivalent ¢rst-row metals 24^26 Zinc
Triphenylphosphine 164 reactions at labile Zn(II) centers 117^118
Tungsten, catalysis by 164 solvent exchange data, divalent state 21

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INDEX

Actinides divalent state 19

Density functional studies of iridium- internal electron transfer in sul¢te

Gold oxidation by sulfur trioxide and redox

Iron binary and ternary cyanide complexes

e¡ect of non-leaving ligands 31 chemical biology examples 237^238

Oxidative activation (Cont.) reaction scheme 167^168

oxidation step mechanisms kinetic competition 170

Rhenium catalysis of oxygen transfer ligand substitution reactions in square-

Template reactions 133 Turnstile mechanism for ligand

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