Chemistry and catalysis advances in organometallic chemistry and catalysis
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710 INDEX
dehydroaryloxylation (see dehydroxygenation), dehydrofluorination, of alkyl fluorides, 55 dehydrogenation, 3, 529–539 dehydroxygenation, of ethyl acetate, 49, 50 of ethyl aryl ethers, 45 of ethyl tosylate, 50 desulfitative catalysis, 295–302 desulfitative cross-coupling, 295–298 desulfitative transformations, 295–296, 300–301 DFT calculations, [2 +2] additions, 308–309, 311 [3 +2] additions, 308–309, 311 electronic energy, 312 energy profile, 45–50, 54, 309, 310 functionalization of alkanes, 18–23 intermediates, 19–22, 307, 308, 310 reaction mechanisms, 18–23, 178, 306–311 redox chemistry of sulfides, sulfoxides and sulfones catalysed by Mo complexes, 305–314 transition states, 20, 308, 310 Wiberg indices, 308, 312 diaminocarbenes, 143–153 diansa-ferrocene, 163, 165 diansa-nickelocene, 163 differential pulse voltammetry, 699 dihydrogen complexes, dihydrogen bonding, 98, 100, 106 heterolytic cleavage, 106, 107 homolytic cleavage, 106, 107 1,2-dihydronaphthalene, 65 dinickelocene, 163 (2,3- η-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium, 11 diphosphites, 426 dipolar cycloaddition, 171–176, 178, 199–204, 459–470 direct self-assembly, 18 donor/acceptor substituent, 510 drug resistance, 575 dye regeneration times, 508 dye sensitized solar cells, 503, 504, 508, 510 EIE (see equilibrium isotope effect), E L Lever ligand parameter, 679–688 electrochemical and ESR studies, 567 electrochemical oxidation, 657, 669–674 electrochemical reduction, 657 electrochemistry, 631–700 electrodes, 655 electroluminescence, 490 electrolysis, 640, 642 electrolysis of water, 518 electrolyte, 504, 505, 509 electron-donating groups, 486, 487 electron donor ability, 678, 679, 685 electron injection, 505, 509 electron recombination, 505, 509 electron transfer, 505, 509, 521, 523–525, 656, 667–674, 694 electron transport ability, 482 electron-richness, 678 electron-transport layer, 490 electron-withdrawing group, 486, 487 enantioselectivity, 230–231, 459–470 encaged metal, 694 encapsulation, 574 endohedral fullerenes, 459, 460 endothelial cells, 546, 547 endotoxic shock, 546 energy,
renewable energy sources, 503 sustainable energy technology, 503 energy gaps, 505 energy levels, 504, 505, 507, 509 epoxidation, 3 EPR (Electron Paramagnetic Resonance) spectroscopy, 229–230, 669, 672, 673 equilibrium isotope effect, 43 esterification, 509 ethylbenzene, 62 ethylnaphthalene, 64 exhaust carbon, 513, 517 external quantum efficiency (EQE), 506 Fe II /Fe III
oxidation, 569 Fermi level, 505 ferricenium cation, 633, 635, 636 ferrocene, 5, 8, 9, 157–158, 160–163, 165–169, 445–447, 451, 454, 456, 566–571, 575, 576, 633–650 ferrocenium (see ferricinium), ferrocenophane, 159–160 transposition, 572 ferrocenophanyl group, 570, 571 ferrocenophanol, 572 ferrocenyl, catechols, 569, 570 redox antenna, 575 redox products, 569 ferrocidiphenol, 571, 572, 574 ferrocifen drugs, 563–576, 633–650 ferrocifen complexes, ferrocenophanes, 643 ferrocenyl acetanilide, 640 ferrocenyl aniline, 640 ferrocenyl catechols, 569, 570, 638–640 ferrociphenol, 635, 636, 638, 640 ferroquine, 566, 567 fill-factor (FF), 504, 508 fine chemicals, 359, 372 Fischer aminocarbene complexes, 653–665 flank benzene ring, 478, 479 flavopiridol, 606, 607 floating catalyst, 446, 449, 452–455 fluorescence, 487–491 α-fluoride elimination, 53 β-fluoride elimination, 54, 55 formaldehyde dehydrogenase, 522 formate dehydrogenase, 522 formic acid, 529, 532, 533, 536–538 fullerenes, 459–470, 473, 474, 476, 478, 479, 691–700 functional groups, 509 β-functionalized isocyanides, 118–119, 121 functionalised N-heterocyclic carbenes, 133–141 functional phosphines, 189–194 functionalization of alkanes (see alkane functionalization), functionalization of carboranes (see carborane functionalization), functionalization of sp 2 carbon, 64, 66 functionalization of sp 3 carbon, 60, 61, 66 functionalized alcohols, 2,3-dihydro-2,2-dimethylbenzofuran-7-ol, 438, 440 INDEX 711 2-(dimethylamino)ethanol, 438, 442 2-methoxyethanol, 438, 443 gaseotransmitter, signaling, 546–548 geraniol, 64–67 glioma, 574, 575 gliosarcoma in rats, 574 glycerol oxidation, catalysts, 248–254 with H 2
2 , 248–254 with tert-butyl hydroperoxide, 252–254 gold catalysis, 207–222 gold catalysts, 207, 210–213, 222, 242–244 green oxidant, 3–10, 15–18, 22, 27–36, 286–291 Grubbs’ catalysts, 157, 161 H/D exchange, 3 half-sandwich complexes, 16, 17, 134, 136–141, 269–282, 609–611, 613, 614, 681 Hammett’s constant, 654 H-donor, 523 healthy cells, 569, 574, 575 Heck reaction, 150–152 heme, free heme, 546, 548 heme oxygenase (HO), 545–549 amplification loop, 547 hemilabile ligand, 667–669, 673, 674 hemilability, 185 hemoproteins, 546, 547, 550 heterocyclic ligands, 507–509 heterogeneous systems, 66, 239–244 heterometallic, 18 heterometallic alkoxide derivatives, synthesis, coordinated alcohols as anchors for organometallics, 438, 440 deoligomerization by cocomplexation, 439 protonation of metallocenes, 440 heteropolyanions, 60 hexanuclear rhodium carbonyl cluster, 11 hole-transport layer, 490 homing peptides, 614 homogeneous catalysis (see catalysis, homogeneous) homogeneous systems, 66 HOMO and LUMO, 98, 653, 654, 659, 662, 692, 694, 697, 698 hormone receptors, 606 hybrid ligands, 185–186 hybrid systems, 525 hydroamination, 372–374 hydrocarboxylation, of alkanes, 20–22, 29, 33–36 metal-free alkane hydrocarboxylation, 20, 21 hydrogen, 422, 425, 426, 432 hydrogen bond, non-classical, 97, 100, 105 formation enthalpy, 101 hydrogen peroxide, 8, 10, 11, 15, 17, 19–23, 59–65, 247–255, 286–293, 307–309 hydrogen storage, 529–539 hydrogen transfer, 139 hydrogenation, 529, 530, 532, 538, 539 hydrosilylation, 139–141 hydrogen-transfer type oxidations of alcohols, 237, 240–241 hydrophosphonylation, 375–376 hydrosoluble complexes, 15–17, 19–23, 27–31, 286–289, 291 hydrosoluble ligands, 15–17, 286, 287 hydroxyalkylisocyanides, 118 hydroxylating agent, 20–21 hydroxyl radical, 6, 8, 10, 11, 19–20, 23 hydroxytamoxifen, 567, 569 IC 50 , 608–610, 613, 614 ICOMC (International Conferences on Organometallic Chemistry), xii, xiii, 703–706 silver/gold jubilee book, xii silver/gold jubilee medal, xii I M electrochemical parameter, 679–681 imidazolin-2-ylidene, 115, 117, 125 in vivo testing, 573 incident photon to current conversion efficiency (IPCE), 504, 506–509 indane, 61 1 H -indene, 61–62, 65 indolo[3,2- c]quinolines complexes, copper, 612–614 osmium-arene, 610, 611, 613, 614 ruthenium-arene, 609–611, 613, 614 indolo[3,2- d]benzazepines complexes, copper, 612–614 gallium, 608, 610 osmium-arene, 610, 611, 613, 614 ruthenium-arene, 609–611, 613, 614 inflammation, 545–548 inhalation, 549, 551, 556 inorganic chemical biology, 563 ischemia-reperfusion, 546, 554 insertion reaction, 91 intensity of the incident light, 508 intermolecular oxidative addition, 40–42 internal quantum efficiency (IQE), 506 intramolecular electron transfer, 636, 641–643, 650, 662 intramolecular hydroamination, 317, 319 intravenous injection, 551, 574 inversion barrier, 475, 476, 481 ion channels, 546, 547, 548, 553, 556 ionic liquids, 424, 529–539 iridium sensitizer, 507 iridium-pincer complexes, 39, 40, 54 iron catalysts, 133–136, 139–140, 234–235, 240, 242 iron complexes, 136–139, 234–236, 286–289, 546, 555 iron N-heterocyclic carbenes, 136–139 iron pentacarbonyl, 446, 451, 453, 455 IR-spectroelectrochemistry, 664 isocyanides, 117–119, 121, 123, 145–153, 171–173, 176–177, 181, 677–679, 682, 683 isomers, 187, 194–195 isotope effects, 43, 53 Kaplan-Meier survival curves, 575 kenpaullone, 607 KIE (see kinetic isotope effect), kinetic isotope effect, 43, 44, 50–52 of alkyl fluoride C-F oxidative addition, 52 of ether C-O oxidative addition, 43, 50 of tosylate C-O oxidative addition, 50 KP1019, 565 labeling studies, 43
712 INDEX
lactide, 359, 370 lactide ring opening polymerization, 317, 321 Lever electrochemical model, 680, 681 ligand design, amido ligands, 316 macrocyclic systems, 316–320 tetraazamarcrocycles, 319 light alkanes, 17, 21, 22, 29, 33, 34, 290, 291 light-driven process, 522 light-independent process, 522 Linear Free Energy Relationship (LFER), 654, 658, 660 lipid bilayers, 633, 634, 644, 648 lipid nanocapsules (LNC), 574–576 long-circulating nanoparticles, 574 long-term survivors, 575 luminescent organoboron compounds, 485–489 macrocyclic functionalization, 321 manganese catalysts, glycerol oxidation, 248–249 materials, organometallic, 379 maximum power, 508 MCF-7 cell lines, 567, 569 McMurry coupling, 566, 572 MDA-MB-231 cell lines, 567–572, 575 mechanisms, alkane carboxylation, 21, 22 alkane hydrocarboxylation, 20, 21 alkane oxygenation, 3–12, 18–20 1,2-dehydroaryloxylation of ethyl aryl ethers, 45 1,2-dehydrofluorination of alkyl C-F bonds, 53 1,2-dehydroxygenation of ethyl acetate, 49 electron transfer induced reactions, 655, 663, 667–670, 673 methanol carboxylation, 260, 262–267 methyl acetate C-O oxidative addition, 43, 47, 48 methyl tosylate C-O oxidative addition, 50, 51 net oxidative addition of alkyl fluoride C-F bonds, 53 net oxidative addition of methyl aryl ether C-O bonds, 43 oxidation of sulfides, 305–314 oxidation and reduction of sulfoxides, 305–314 mechanochemistry, 493–498 medicinal chemistry, 557, 566
metal catalysis (see catalysis) metal catalysts and complexes, alkaline earths (see alkaline earths) aluminium 20, 440 barium 441 bismuth 495 boron 74–78, 81–94 carbonyls for CO based therapies (see CO based therapies) chromium 122, 656 cobalt 18, 73–78, 510 copper (see copper catalysts, copper complexes) gallium 608 gold 118, 121, 207–223 indium 441 iridium 5, 39–55, 118, 121, 126, 274, 278–280, 387, 506, 507, 671 iron 5–7, 16–18, 124, 136–140, 235–238, 288, 506, 507, 656 (see
manganese 61, 62, 64–67, 116, 119, 249 molybdenum 7, 102–106, 122, 124, 158, 305–312, 551, 553, 558 nickel 81–89, 92–93, 100, 104, 136–141, 163, 167, 187, 188, 190 organometallic 445–451, 454 osmium 10, 248–250, 506–508, 669 palladium 86–88, 119, 128, 145–152, 176, 193, 236, 238, 386, 463 platinum 4, 123, 128, 173–175, 188, 189, 195, 384, 387, 506, 507 polyoxometalates 59, 60, 62, 63 rare earths 345–357, 621, 624 rhenium 18, 116, 287, 290–292, 506, 507, 549, 554, 589, 591–594 rhodium 11, 12, 127, 237, 239, 241, 259–268, 260–266, 274, 278, 280, 462 ruthenium 106, 116, 117, 125–127, 158, 237, 241, 270–282, 447, 503, 505, 506, 508–510, 536–538, 564, 565, 582, 583, 609–611, 613, 614, 672 scorpionates 15–17, 272–277, 285–293, 683 silver 384–386, 389, 390, 466, 495 technetium 549, 589–602 titanium 442 tungsten 102–106, 121–124, 656 vanadium 12, 17–22, 227–231, 286, 289, 291 zinc 441, 508 zirconium 88–94, 315–322 metal complex redox mediators 508 metal to ligand charge transfer (MLCT), 505, 509 metal nanoparticles, 533, 535 metal oxides, 239, 241 α−metallation, 118 metallocenes, 88–94, 157–169 (see also ferrocene) metallocene dichlorides, 165, 169 metallodrugs, 493–496, 498, 564, 565, 581, 584–586 metalloenzymes, 563, 564 metallofullerenes, 691–700 metal-organo catalysis (see catalysis), metallopharmaceuticals, 493–498 metalloporphyrins, 59, 60, 64–66, 68 metallothionein mimic, 300 Metal Organic Frameworks (MOFs), 382, 408–409 metastases, 575 metathesis, 157–169 (see also ring opening metathesis) methanol carbonylation, 259–268 methylidene formation, 45, 48, 53 M-H bond, activation, 97, 102 heterolytic splitting, 100, 103 polarization, 98, 100, 103 micro-emulsion, 574 microwave assisted oxidations, 233–244 migration, acetate, 48–50 aryloxide, 43 hydride, 48, 50, 53 mitogen-activated protein kinases (MAPKs), 547 mixed sandwich complexes, 681 modified semiconductors, 523 molecular engineering, 504, 509 molecular imaging, contrast enhancement, 620 magnetic resonance imaging, 619, 620 molecules with two redox centers, 655 molybdenum catalysis, CpMo(CO) 3 X, 306–307 hydride complexes, 308, 311 MoO
2 Cl 2 , 306–311 monoterpenes, 64, 65 MRI contrast agents, 619–628 MTT assay, 611, 613, 614 multicopper complexes and coordination polymers, aminoalcohols, 28, INDEX 713 N,O-ligands, 29, 30, 36 self-assembly synthesis, 17, 27, 28, 30, 410–418 water-soluble compounds, 15–19, 27–30, 33, 286–289 multicatalysis, 325–339 multinuclear assemblies, 17, 27–31 myocardial infarct, 548, 550, 552 N 3 dye, 506, 509 N-alkylimidazoles, 115 NAMI-A, 565 nanocapsules, 573, 574 nanoparticles, cobalt, 422, 429–433 drug delivery vehicles, 626 iron, 428 iron oxide, 624, 626, 627 lipid-based, 626, 627 lipid microbubles, 627 lipid microspheres, 627 liposomes, 626, 627 magnetic, 422, 428–433 metal, 421, 422, 426 oily suspensions, 627 organometallic, 421–434 quantum dots, 626, 628 ruthenium, 422–428 solid lipid nanoparticles, 627 yeast cell wall particles (YCWPs), 627 nanoreactors, 422–423 nanotechnology, 619, 628 naphthalene, 62, 65 nerol, 64 N-heterocyclic carbenes, 113–129, 133–141, 145–153, 238, 330–333, 336–337, 339 N-heterocyclic carbene palladium catalysts, 145–153, 236–239 nickel, 81–89, 92–93, 136–141 nickel alkoxides, 140 nickel catalysts, 139–141 nickel N-heterocyclic carbenes, 138–141 nickelocene, 163, 167 nitric oxide synthase (NOS), 547, 552, 555 nitriles, 172–181, 679 Nobel prizes, xi non-innocent ligand, 667–670, 673, 674 non-planar π-conjugated carbon system, 473, 479 nuclear imaging, 589, 591 nuclear medicine, 589, 591, 600 octahedral-type complexes, 677, 678, 681 OLEDs, 490, 491 olefin metathesis, acyclic diene (ADMET), 157–158, 160, 165 alkyne cross metathesis, 168 cross metathesis (CM), 160, 165–167 enantioselective RCM, 162 ring-closing (RCM), 161–163 ring opening polymerization (ROMP), 157–160, 391 open circuit voltage, 504, 506, 508, 510 open geodesic polyarene, 473 organic light-emitting diodes (see OLEDs) organoboron compounds, 485–491 organometallic, anti-cancer agents (see anti-cancer drugs) catalysis (see catalysis) chemical biology 563, 564 complexes (see metal catalysts and complexes) hydrogenases 563 polymer properties biological 391 catalytic 391, 395, 398, 400 electronic 382–393, 397–399 photovoltaic 383 quinone methides 568 othometalation 319 over-potential, 524 oxaliplatin, 605, 606 oxazoline based ligands, 185–189, 191–194 oxidant, 59–67 oxidation catalysis, alcohols, 233–244 alkanes to alcohols and ketones, 5–11, 15–20, 31, 32, 60, 63, 66, 286–290, 415 alkanes to carboxylic acids, 20–22, 286, 288, 290–291 glycerol to carbonyl compounds, 248–253 glycerol to dihydroxyacetone (DHA), glycolic acid and hydroxypyruvic acid, 249–254 ketones (see Baeyer-Villiger reaction) sulfides to sulfoxides and sulfones 305–314 sulfoxides to sulfones 305–314 oxidation potential 654 oxidation state, 667, 669, 670, 674, 694, 695, 697, 698, 700 oxidation with hydrogen peroxide, 234, 236, 240, 242–244, 305–314, 415 oxidation with tert -butyl hydroperoxide, 3, 5, 8, 11, 67, 234, 305–314 oxidative addition, of azoles, 124–125, 127 of alkyl fluoride C-F bonds, 51–53 of ether C-O bonds, 40, 42, 44 of ester C-O bonds, 45, 50 of tosylate C-O bonds, 50 (PCP)Ir (see iridium-pincer complexes) P,N chelating ligands, 185–194 palladium, 85–87 palladium catalysts, 145–153, 236, 238 palladium(II) complexes, 145–153, 236 palladium-catalyzed desulfitative coupling, 295–299 PARP-1 inhibithor, 585, 586 PEG (polyethylene glycol) chains, 574, 575 perfusion agents, 590, 593 Periana system, 3, 4 peroxidative halogenations, 22 peroxidative oxidation, 286, 289–291, 293, 305–314, 415 (see also hydrogen peroxide) peroxydisulfate, for alkane carboxylation, 8, 9, 20–22, 35 phenanthrene, 65 phenol functions, 569, 573, 576 phenylazo-pyrazoles, 277–278 phosphines, 187, 189–194 phosphonate groups, 509 photoactive materials, 522 photoautotrophs, 522 photocatalysis, 329 photocathode surface, 525 photochemical stability, 506 photochemical systems, 524 photoelectrochemical reduction, 524 photoelectrochemical systems, 525 714 INDEX
photoexcitation of dye, 505 photoisomerization, 490 photoluminescence, 486 photoresponsive materials, 485, 490 photosensitizer, 505, 506, 510, 521, 524 photosynthesis, synthetic, 513–525 photovoltaic (PV), 519 piano stool structures, 582 Pickett electrochemical model, 677–679, 683, 686 pinacol, 572, 573, 576 pincer complexes, 39 P L electrochemical ligand parameter, 677–679 planar chirality, 168 platinum drug, carboplatin, 564, 605, 606 cisplatin, 564, 565, 574, 575, 605, 606 oxaliplatin, 564 polarizability, 678, 687 poly(pyrazolyl)alkanes, 276, 286–289, 291 poly(pyrazolyl)borates, 270, 272–277, 280 polycyclic aromatic hydrocarbons, 62, 64 polyfunctional ligands, 185 polymers, coordination, 17, 18, 28–31, 382, 407–417 metal fullerene, 385–386 metal graphene, 397 metal-backbone organometallic, 382 metal-side organometallic, 390–397 organometallic, 381–400 properties (see organometallic polymer properties) tailor made 345 polymerization coordinative chain transfer, 345–357 copolymerizations, 345–357 ring opening metathesis (ROMP), 157–160, 391 ring opening (ROP), 359–376, 391, 395–397, 399 polynuclear boron complexes, 487 polyoxometalates (see metal catalysts and complexes) polyphenols, 573, 574 poly(vinylpyrrolidone) (PVP), 422, 423, 425, 430 porosity, without pores, 416–417 sorption, 408, 416 porphyrins, 59–67, Positron Emission Tomography (PET), 590, 591 power conversion efficiencies, 504, 507, 508, 510 proapoptotic compounds, 575 protic NHCs, 115, 117 proton transfer, activation free energy, 101 energy profile, 103, 106 enthalpy, 101 entropy, 101 solvent effect, 104–105 p-type semiconductor, 524 pyrazine-2-carboxylic acid (PCA or Hpca), 5, 19, 20 pyrazole based ligands, 269–270, 277–278 quantum yield, 486–489 quasi-borinium cation, C-H bond activation, 74–75 C-X bond activation, 76 Lewis acidity, 77 quasi-reversibility, 655 quinone, 667–673 quinone methide, 567–572, 576 radical, 6, 7, 10–12, 19–22, 32–35, 667, 669, 670 radical mechanism, 19, 21, 22, 32–35, 286, 290–291 radionuclide therapy, 589, 591 radiopharmaceuticals, 564, 589–592, 596, 600, 601 rare earths catalysts, 345–348, 351, 354 rate-determining-step, 260–262 reactive oxygen species (ROS), 546, 547 redox, 305–314, 566, 569, 575 redox inactive, 19–20 redox mediator, 504, 505, 508, 510 redox potential, 691, 694, 695, 697 redox potential-structure relationships, 677–688 redox potential parameterization, 677, 687 redox properties and processes, 633–650, 653, 657, 658, 660, 662, 664, 667–674, 692, 694, 695, 698, 699 red-shift, 486 reduction, 670–674 reduction of sulfoxides, 140, 305–314 reduction potential, 654 reduction reactions, 139–141 reductive elimination, 43, 51, 259–268 reductive elimination mechanism, 264–266 relay catalysis, 326, 338 relay and sequential, 326, 334–335 retro-cycloadditions, 463–465 rhenium catalysts (see metal catalysts and complexes) rhodium catalysts (see metal catalysts and complexes) ribonucleotide reductases, 606 ring-opening polymerization, 359–360, 363, 365–372 ROS (Reactive Oxygen Species), 567, 569, 572, 576 Ru albumin, 584 ruthenium, anticancer compounds, 581–586 catalysts (see metal catalysts and complexes) complexes (see metal catalysts and complexes) CO-Releasing Molecules (CORMs) 549–551 sacrificial donors, 521 Salvarsan, 605 sandwich complexes, 15, 680, 681
Secondary Building Unit (SBU), 408, 411–412, 415, 417 Schrock catalyst, 166–167 scorpionate complexes (see metal catalysts and complexes) self-assembly synthesis, 17, 27, 28, 30 semiconductor, SnO 2
TiO 2 , 505 ZnO, 504–507, 509 sensitization, 509 semiquinone, 668–670, 672, 673 senescence, 565, 569, 575, 576 sensitizers, 506–510 sensory materials, 485 sequential catalysis, 326, 334–335 serendipity, 407–418 shaped carbon materials, 445, 446, 448, 449, 454 Shilov chemistry, 3 short circuit current, 504, 506, 508 silica nanoparticles, 67 Single Photon Emission Computed Tomography (SPECT), 590, 591, 596, 599, 601 |
