Electron transfer in chemistry: 2 Organic molecules, organometallic and inorganic molecules
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2001
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| Beschreibung: | XLVII, 1002 S. Ill., graph. Darst. |
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| 245 | 1 | 0 | |a Electron transfer in chemistry |n 2 |p Organic molecules, organometallic and inorganic molecules |c Vincenzo Balzani (ed.) |
| 264 | 1 | |a Weinheim [u.a.] |b Wiley-VCH |c 2001 | |
| 300 | |a XLVII, 1002 S. |b Ill., graph. Darst. | ||
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| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 650 | 4 | |a Oxidation-reduction reaction | |
| 700 | 1 | |a Balzani, Vincenzo |d 1936- |e Sonstige |0 (DE-588)10907811X |4 oth | |
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| adam_text | VINCENZO BALZANI (ED.) ELECTRON TRANSFER IN CHEMISTRY ORGANIC MOLECULES
ORGANOMETALLIC AND INORGANIC MOLECULES WILEY-VCH WEINHEIM * NEW YORK *
CHICHESTER BRISBANE * SINGAPORE * TORONTO 2 XIV CONTENTS VOLUME II PART
1 ORGANIC MOLECULES 1 JOCHEN MATTAY (ED.) 1 REACTIVITY PATTERNS OF
RADICAL IONS*A UNIFYING PICTURE OF RADICAL-ANION AND RADICAL-CATION
TRANSFORMATIONS 5 MICHAEL SCHMITTEL AND MANAS K. GHORAI 1.1 INTRODUCTION
5 1.2 A UNIFYING PICTURE OF RADICAL-ANION AND RADICAL-CATION CHEMISTRY 5
1.3 A CONSTRUCTION SET OF ELECTROPHORES AND ITS RELEVANCE FOR DEVISING
SELECTIVE REACTIONS VIA RADICAL IONS 7 1.4 REDUCTIVE AND OXIDATIVE
BOND-CLEAVAGE REACTIONS 14 1.4.1 GENERAL PRINCIPLES OF BOND CLEAVAGE 14
1.4.2 SYNTHETIC, KINETIC AND THERMODYNAMIC ASPECTS OF REDUCTIVE BOND
CLEAVAGE 17 1.4.3 SYNTHETIC, KINETIC AND THERMODYNAMIC ASPECTS OF
OXIDATIVE BOND CLEAVAGE 23 1.5 REDUCTIVE AND OXIDATIVE BOND-FORMATION
REACTIONS 29 1.5.1 GENERAL PRINCIPLES OF BOND FORMATION 29 1.5.2
SYNTHETIC, KINETIC AND THERMODYNAMIC ASPECTS OF REDUCTIVE BOND-FORMATION
29 1.5.3 SYNTHETIC, KINETIC, AND THERMODYNAMIC ASPECTS OF OXIDATIVE
BOND-FORMATION 33 1.6 PERICYCLIC REACTIONS 37 1.6.1 GENERAL PRINCIPLES
OF PERICYCLIC REACTIONS 37 1.6.2 SYNTHETIC, KINETIC AND THERMODYNAMIC
ASPECTS 38 1.7 CONCLUSION 40 ACKNOWLEDGMENTS 40 REFERENCES 40 2 ELECTRON
TRANSFER FROM ALIPHATIC AND ALICYCLIC COMPOUNDS 55 HEINZ D. ROTH 2.1
INTRODUCTION 55 2.2 ELECTRON-TRANSFER REACTIONS OF ALIPHATIC COMPOUNDS
56 2.2.1 HIGH-ENERGY IRRADIATION OF MATRICES 56 2.2.2 ELECTRON SPIN
RESONANCE 57 2.2.3 ELECTRON-TRANSFER REACTIONS OF METHANE 59 2.2.4
ELECTRON-TRANSFER REACTIONS OF -ALKANES 61 2.2.5 DEPROTONATION OF
W-ALKANE RADICAL CATIONS 66 2.2.6 ELECTRON-TRANSFER REACTIONS OF
BRANCHED ALKANES 68 2.2.7 ELECTRON TRANSFER FROM ALKANES TO ZEOLITES 69
2.3 ELECTRON-TRANSFER REACTIONS OF CYCLOALKANES 71 2.3.1 ELECTRON
TRANSFER FROM C3-C8 PROTOTYPE CYCLOALKANES 72 CONTENTS XV 2.3.2
CYCLOPROPANE RADICAL CATIONS 77 2.3.3 ELECTRON-TRANSFER REACTIONS OF
SUBSTITUTED CYCLOBUTANE SYSTEMS 97 2.3.4 ELECTRON-TRANSFER REACTIONS OF
CYCLOALKANES IN ZEOLITES 99 2.4 ELECTRON-TRANSFER REACTIONS OF BICYCLIC
SYSTEMS 100 2.4.1 ELECTRON TRANSFER OF STRAINED BICYCLIC SYSTEMS 101
2.4.2 ELECTRON TRANSFER OF UNSTRAINED BICYCLIC SYSTEMS 116 2.4.3
ELECTRON-TRANSFER CHEMISTRY OF BICYCLIC AND HIGHER RING SYSTEMS... 118
2.4.4 TRIPLET RECOMBINATION OF RADICAL ION PAIRS 124 2.4.5 CONCLUDING
REMARKS 126 REFERENCES 127 3 THE ELECTRON-TRANSFER CHEMISTRY OF
CARBON-CARBON MULTIPLE BONDS . 133 NATHAN L. BAULD AND DAXIN GAO 3.1
INTRODUCTION 133 3.2 ELECTRON TRANSFER CHEMISTRY INVOLVING C-C MULTIPLE
BONDS AS SINGLE-ELECTRON DONORS 134 3.2.1 DISCOVERY OF CATION RADICALS
134 3.2.2 A MOLECULAR-ORBITAL PICTURE OF CATION RADICAL FORMATION 135
3.2.3 CATION RADICAL STRUCTURES 136 3.2.4 THE GENERATION OF CATION
RADICALS IN SOLUTION 138 3.2.5 CATION RADICAL CYCLOBUTANATION 141 3.2.6
FORMATION OF 1,2-DIOXETANES BY CATION RADICAL ADDITIONS TO TRIPLET
DIOXYGEN 147 3.2.7 CATION RADICAL DIELS-ALDER CYCLOADDITIONS 147 3.2.8
CATION RADICAL DIELS-ALDER CYCLOADDITIONS TO DIOXYGEN 160 3.2.9
MECHANISMS OF FORMATION OF SUBSTRATE CATION RADICALS FROM THE AMINIUM
SALT 160 3.2.10 NEUTRALIZATION OF THE PRODUCT CATION RADICAL 163 3.2.11
MECHANISTIC DIAGNOSIS OF CATION RADICAL CYCLOADDITIONS 165 3.2.12
ABSOLUTE REACTION RATES AND CATION RADICAL PROBES 167 3.2.13 GENERAL
THEORETICAL CONSIDERATIONS IN CATION RADICAL CYCLOADDITIONS 169 3.2.14
CALCULATIONAL RESULTS 170 3.2.15 NATURAL PRODUCT SYNTHESIS AND SYNTHETIC
METHODOLOGY USING CATION RADICAL CYCLOADDITION REACTIONS 171 3.2.16
CATION RADICAL POLYMERIZATION 172 3.2.17 THE CATION RADICAL
VINYLCYCLOBUTANE (VCB) REARRANGEMENT 173 3.2.18 THE CATION RADICAL
PHENYLCYCLOBUTANE REARRANGEMENT 175 3.2.19 THE CATION RADICAL
VINYLCYCLOPROPANE REARRANGEMENT 176 3.2.20 CATION RADICAL CHAIN
CYCLOPROPANATION 177 3.2.21 CATION RADICAL CYCLOADDITIONS FORMING
FIVE-MEMBERED RINGS 179 3.2.22 THE CATION RADICAL COPE REACTION 180
3.2.23 A [1,16] SIGMATROPIC SHIFT 182 3.2.24 ELECTROCYCLIC REACTIONS OF
CATION RADICALS 182 3.2.25 CATION RADICAL CYCLIZATIONS 184 3.2.26 OTHER
REACTIONS OF CATION RADICALS 186 XVI CONTENTS 3.3 ELECTRON TRANSFER
CHEMISTRY INVOLVING C-C MULTIPLE BONDS AS SINGLE ELECTRON ACCEPTORS 188
3.3.1 THE THREE-ELECTRON BOND OF THE ETHENE ANION RADICAL 188 3.3.2 THE
SHAPE OF THE SOMO OF A PI ANION RADICAL 189 3.3.3 THE BUTADIENE ANION
RADICAL 190 3.3.4 DISPROPORTIONATION OF ANION RADICALS TO DIANIONS AND
NEUTRAIS 190 3.3.5 DIANION RADICALS, TRIANION RADICALS, AND MULTIANION
RADICALS 191 3.3.6 METHODS FOR GENERATING ANION RADICALS 192 3.3.7 THE
BIRCH REDUCTION OF NON-TERMINAL ALKYNES 193 3.3.8 BIRCH REDUCTION OF
CONJUGATED DIENES 194 3.3.9 COUPLING OF ANION RADICALS 195 3.3.10
INTRAMOLECULAR CYCLIZATIONS INVOLVING ANION RADICALS 196 3.3.11
PERICYCLIC REACTIONS OF ANION RADICALS 199 3.4 ELECTRON TRANSFER
REACTIONS OF C-C MULTIPLE BONDS WHICH INVOLVE BOTH SINGLE ELECTRON
DONATION AND ACCEPTANCE 202 3.4.1 REACTIONS INVOLVING BOTH ANION
RADICALS AND CATION RADICALS 202 ACKNOWLEDGMENT 202 REFERENCES 202 4
ELECTRON-TRANSFER REACTIONS OF AROMATIC COMPOUNDS 206 GEORG GESCHEIDT
AND MD. NADEEM KHAN 4.1 INTRODUCTION 206 4.2 COMPUTATIONAL METHODS FOR
ORGANIC RADICALS 207 4.3 ION PAIRING 209 4.4 RADICAL CATIONS 211 4.4.1 N
SYSTEMS 211 4.4.2 OLEFINS 226 4.4.3 HETERONUCLEAR RADICAL CATIONS 230
4.5 RADICAL ANIONS 235 4.5.1 % SYSTEMS 235 4.5.2 ALKENES 248 4.5.3
HETERONUCLEAR RADICAL ANIONS 250 4.6 SO WHAT?*CONCLUSIONS AND OUTLOOK
254 REFERENCES 254 5 ELECTRON-TRANSFER CHEMISTRY OF FULLERENES 270
SHUNICHI FUKUZUMI AND DIRK M. GULDI 5.1 INTRODUCTION 270 5.2 FUNDAMENTAL
ELECTRON-TRANSFER PROPERTIES OF FULLERENES 272 5.3 THERMAL ELECTRON
TRANSFER 275 5.3.1 RADIOLYTICALLY GENERATED RADICAL SPECIES 275 5.3.2
ELECTRON-TRANSFER REACTIONS OF FULLERENE ANIONS 282 5.4 INTERMOLECULAR
PHOTOINDUCED ELECTRON TRANSFER 290 5.4.1 FORMATION OF FULLERENE RADICAL
ANIONS 291 5.4.2 SELECTIVE TWO-ELECTRON REDUCTION 294 5.4.3 C-C BOND
FORMATION VIA PHOTOINDUCED ELECTRON TRANSFER 296 CONTENTS XVII 5.5
INTRAMOLECULAR PHOTOINDUCED ELECTRON TRANSFER 305 5.5.1 FULLERENE
ELECTRON-DONOR SYSTEMS 305 5.5.2 FULLERENE ELECTRON-ACCEPTOR SYSTEMS 309
5.5.3 FULLERENE CHROMOPHORE SYSTEMS 310 5.6 OXIDATION OF FULLERENES 323
5.6.1 GAS-PHASE OXIDATION 323 5.6.2 OXIDATION OF FULLERENES IN SOLUTION
323 5.7 SUMMARY 325 ACKNOWLEDGMENT 326 REFERENCES 326 6
ELECTRON-TRANSFER REACTIONS OF HETEROAROMATIC COMPOUNDS 338 ANGELO
ALBINI AND MAURIZIO FAGNONI 6.1 INTRODUCTION 338 6.2 STRUCTURE OF THE
RADICAL IONS OF HETEROAROMATIC COMPOUNDS 339 6.2.1 RADICAL CATIONS 339
6.2.2 RADICAL ANIONS 341 6.2.3 STAHLE RADICAL IONS 342 6.3 CHEMICAL
REACTIONS VIA ELECTRON TRANSFER*THE HETEROAROMATIC COMPOUND IS THE DONOR
342 6.3.1 GENERAL SCHEME 342 6.3.2 ELECTRON AND PROTON TRANSFER 344
6.3.3 RING OPENING AND REARRANGEMENT 345 6.3.4 COUPLING, DIMERIZATION,
AND POLYMERIZATION 346 6.3.5 FUNCTIONALIZATION OF THE RING 350 6.3.6
CYCLOADDITIONS 360 6.3.7 OXYGENATION 360 6.4 CHEMICAL REACTIONS VIA
ELECTRON TRANSFER*THE HETEROAROMATIC IS THE ACCEPTOR 361 6.4.1 GENERAL
SCHEME 361 6.4.2 RING OPENING AND REARRANGEMENT 362 6.4.3 COUPLING,
DIMERIZATION AND POLYMERIZATION 363 6.4.4 DIRECT RING FUNCTIONALIZATION
364 6.4.5 CLEAVAGE OF A GROUP 367 6.4.6 SUBSTITUTION OF A GROUP 369
6.4.7 CYCLOADDITION 371 6.4.8 RING REDUCTION 372 6.5 CONCLUSIONS AND
OUTLOOK 373 ACKNOWLEDGMENT 373 REFERENCES 373 7 ELECTRON-TRANSFER
REACTIONS OF AMINES 379 SURESH DAS AND VELATE SURESH 1. 1 INTRODUCTION
379 7.2 MECHANISTIC STUDIES 379 7.2.1 THERMAL OXIDATION 380 XV111
CONTENTS 7.2.2 ELECTROCHEMICAL OXIDATION 381 7.2.3 RADIATION CHEMICAL
STUDIES OF AMINES 383 7.2.4 PHOTOINDUCED ELECTRON TRANSFER 389 7.2.5
ELECTRON-TRANSFER REACTIONS OF AMINES IN BIOCHEMICAL SYSTEMS 402 7.3
SYNTHETIC APPLICATIONS 411 7.3.1 THERMAL METHODS 411 7.3.2
ELECTROCHEMICAL METHODS 418 7.3.3 PHOTOINDUCED ELECTRON-TRANSFER
REACTIONS 427 ACKNOWLEDGMENT 448 REFERENCES 448 8 ELECTRON-TRANSFER
REACTIONS OF CARBONYL COMPOUNDS 457 AXEL G. GRIESBECK AND STEFAN
SCHIEFFER 8.1 GENERATION OF CARBONYL RADICAL IONS BY ELECTRON TRANSFER
457 8.1.1 ELECTROCHEMICAL GENERATION OF CARBONYL RADICAL ANIONS 457
8.1.2 CHEMICAL GENERATION OF CARBONYL RADICAL ANIONS 462 8.1.3
PHOTOCHEMICAL GENERATION OF CARBONYL RADICAL ANIONS 472 8.1.4 GENERATION
OF CARBONYL RADICAL CATIONS 485 8.2 REACTIVITY PATTERN OF CARBONYL
RADICAL IONS 487 REFERENCES 489 9 ELECTRON TRANSFER IN RADICALS 494
MASSIMO BIETTI AND STEEN STEENKEN 9.1 INTRODUCTION 494 9.2 OXIDATION OF
S BY X (ET BY ADDITION-ELIMINATION (THE AD-EL MECHANISM) 495 9.2.1 S
= ALKENE 495 9.2.2 S = X-C-C-H (ACTIVATION BY H-ABSTRACTION) 501 9.2.3 S
= AROMATIC (AR) 511 9.3 INTRAMOLECULAR ELECTRON TRANSFER WITH BOND
FORMATION 517 9.4 REDUCTIONOFSBYX ,X = E-C (E = HETERO ATOM) 519 9.5
INTRAMOLECULAR ELECTRON TRANSFER ACCOMPANIED BY BOND CLEAVAGE IN RADICAL
IONS 519 9.5.1 OXIDATIVE BOND-CLEAVAGE PROCESSES 520 9.5.2 REDUCTIVE
BOND-CLEAVAGE PROCESSES 558 REFERENCES 571 PART 2 ORGANOMETALLIC AND
INORGANIC MOLECULES 581 DIDIER ASTRUC (ED.) 1 REFLECTIONS ON THE
TWO-STATE ELECTRON-TRANSFER MODEL 583 BRUCE S. BRUNSCHWIG AND NORMAN
SUTIN 1.1 INTRODUCTION 583 1.2 ZERO-ORDER ENERGY SURFACES 584 1.3
SEMICLASSICAL TREATMENT 587 CONTENTS XIX 1.3.1 FIRST-ORDER ENERGY
SURFACES 587 1.3.2 RATE CONSTANT EXPRESSIONS 593 1.3.3 REORGANIZATION
PARAMETERS 594 1.3.4 OPTICAL CHARGE TRANSFER 600 1.4 QUANTUM MECHANICAL
TREATMENT 606 1.4.1 THE ELECTRONIC COUPLING ELEMENT 607 1.4.2 THE
THERMALLY AVERAGED FRANCK-CONDON FACTOR 609 1.5 CONCLUSIONS 615
ACKNOWLEDGMENTS 616 REFERENCES 616 2 CHARGE-TRANSFER INTERACTIONS AND
ELECTRON-TRANSFER-ACTIVATED REACTIONS OF ORGANOMETALLIC COMPLEXES 618
STEPHAN M. HUBIG AND JAY K. KOCHI 2.1 INTRODUCTION 618 2.2
ORGANOMETALLIC COMPLEXES AS ELECTRON DONORS OR ACCEPTORS 620 2.2.1
ORGANOMETALLIC DONORS 621 2.2.2 ORGANOMETALLIC ACCEPTORS 625 2.3
ELECTRON DONOR-ACCEPTOR INTERACTIONS 625 2.3.1 FORMATION OF
ORGANOMETALLIC EDA COMPLEXES 626 2.3.2 UV-VIS SPECTROSCOPIC EVIDENCE FOR
CHARGE-TRANSFER INTERACTIONS IN ORGANOMETALLIC EDA COMPLEXES 628 2.3.3
STRUCTURAL CHANGES DUE TO CHARGE TRANSFER AND/OR ION PAIRING IN
ORGANOMETALLIC EDA COMPLEXES 632 2.4 ELECTRON-TRANSFER INTERMEDIATES IN
ORGANOMETALLIC REACTIONS 636 2.4.1 CHARGE-TRANSFER EXCITATION OF
ORGANOMETALLIC EDA COMPLEXES FOLLOWED BY EFFICIENT BACK ELECTRON
TRANSFER 637 2.4.2 CHARGE-TRANSFER ACTIVATED REACTIONS OF ORGANOMETALLIC
EDA COMPLEXES 640 2.5 INNER-SPHERE AND OUTER-SPHERE MECHANISMS FOR
ELECTRON TRANSFER... 662 2.5.1 ELECTRON-TRANSFER REACTIONS OF
ALKYLMETALS 664 2.5.2 STERIC CONTROL OF INNER-SPHERE OR OUTER-SPHERE
ELECTRON TRANSFERS .. 668 2.6 CONCLUDING REMARKS 670 ACKNOWLEDGMENT 671
REFERENCES 671 3 THE THERMODYNAMICS OF ORGANOMETALLIC SYSTEMS INVOLVING
ELECTRON-TRANSFER PATHS 677 MATS TILSET 3.1 INTRODUCTION 677 3.2
INTRODUCTION TO ELECTROCHEMICAL CYCLES IN THE STUDY OF BOND-CLEAVAGE
REACTIONS OF MOLECULES AND IONS 678 3.3 ABSOLUTE BOND-DISSOCIATION
ENERGIES FOR M-H, COORDINATED LIGAND C-H, AND M-M BONDS 680 3.3.1
THERMOCHEMICAL CYCLE FOR DETERMINATION OF ABSOLUTE M-H BOND-DISSOCIATION
ENERGIES 680 CONTENTS 3.3.2 M-H BOND-DISSOCIATION ENERGIES DETERMINED IN
ACETONITRILE 682 3.3.3 M-H BOND-DISSOCIATION ENERGIES DETERMINED IN
SOLVENTS OTHER THAN ACETONITRILE 684 3.3.4 DISCUSSION OF LIGAND EFFECTS
ON M-H BDE DATA 690 3.3.5 C-H BOND-DISSOCIATION ENERGIES OF COORDINATED
LIGANDS 693 3.3.6 METAL-METAL BDES FROM REDOX EQUILIBRIUM AND ELECTRODE
POTENTIAL MEASUREMENTS 695 3.4 METAL-HYDRIDE CATION RADICAL ACIDITIES
696 3.5 METAL-HYDRIDE BOND-DISSOCIATION ENERGIES IN CATION RADICALS 698
3.6 METAL-HALIDE BOND ENERGIES 701 3.7 BONDING OF 2-ELECTRON DONOR
LIGANDS IN 18- AND 19-ELECTRON COMPLEXES 703 3.8 CHANGES IN LIGAND C-H
BOND STRENGTHS INDUCED BY ELECTRON TRANSFER 705 3.8.1 BENZYLIC C-H BONDS
OF 7I-COORDINATED ARENES 705 3.8.2 A- AND SS-C-H BONDS IN METAL ALKYLS
707 3.8.3 BRIDGING ALKYLIDYNE LIGANDS IN DINUCLEAR COMPLEXES 709 3.9
CONCLUDING REMARKS 710 ABBREVIATIONS 711 REFERENCES 711 4
ELECTRON-TRANSFER REACTIONS OF ELECTRON-RESERVOIR COMPLEXES AND OTHER
MONOELECTRONIC REDOX REAGENTS IN TRANSIRION-METAL CHEMISTRY 714 DIDIER
ASTRUC 4.1 INTRODUCTION 714 4.2 STANDARD REDOX POTENTIALS AND
COMPLEMENTARY REFERENCES 715 4.3 REDUCTANTS 717 4.3.1 ALKALI- AND OTHER
METALS; AMALGAMS AND ALLOYS 717 4.3.2 AROMATIC RADICAL ANIONS AND ANIONS
723 4.3.3 HYDRIDES, GRIGNARD REAGENTS, METAL-ALKYLS AND METAL-ARYLS, AND
OTHER REDUCTANTS 727 4.3.4 MISCELLANEOUS REDUCTANTS 731 4.3.5
METALLOCENES AND BIS-ARENE METAL SANDWICHES 732 4.4 OXIDANTS 745 4.4.1
FE 111 SANDWICH COMPLEXES: FERROCENIUM SALTS [FECP 2 ][X] AND [FECPV-C 6
ME 6 )][SBX 6 ] 2 746 4.4.2 SILVER(I) SALTS 747 4.4.3 COPPER(II) SALTS
748 4.4.4 IRON(III) CHLORIDE 749 4.4.5 CERIUM(IV) AMMONIUM NITRATE (CAN)
749 4.4.6 MISCELLANEOUS HIGH-OXIDATION-STATE INORGANIC COMPLEXES 749
4.4.7 NITROSONIUM SALTS, [NO]X 750 4.4.8 PHOSPHORUS, ARSENIC, AND
ANTIMONY PENTAHALIDES AND ALUMINUM TRICHLORIDE 751 4.4.9 DIOXYGENYL
CATION, 0 2 + , DIOXYGEN O2, AND SUPEROXIDE ANION 0 2 * _ . . 752
4.4.10 HALOGENS: CL 2 , BR 2 , AND I 2 753 CONTENTS XXI 4.4.11
ARENEDIAZONIUM, [N 2 ARYL] + 753 4.4.12 ACIDS 754 4.4.13 TRIARYLAMINIUM
CATIONS, [N(ARYL) 3 ]* + 755 4.4.14 THIANTHRENE RADICAL CATION 757
4.4.15 CARBOCATIONS: TRITYL, [C(ARYL)3] + , SALTS AND SALTS OF OTHER
CARBOCATIONS 757 4.4.16 TCNE, TCNQ, AND OTHER CYANOCARBONS 759 4.4.17
MISCELLANEOUS ORGANIC OXIDANTS 760 4.5 ELECTRON-TRANSFER-CHAIN (ETC)
CATALYSIS 761 4.5.1 HISTORICAL BACKGROUND, MAIN TYPES OF REACTION, AND
PRINCIPLE 761 4.5.2 THE ELECTRON-RESERVOIR COMPLEXES [FE CP(?7 6
-ARENE)] AS ETC CATALYSTS 763 4.5.3 THE FERROCENIUM SALTS AS ETC
CATALYSTS 775 4.6 REDOX CATALYSIS 782 4.6.1 PRINCIPLE OF REDOX CATALYSIS
OF ELECTROCHEMICAL REACTIONS 782 4.6.2 CATALYSIS OF CATHODIC REDUCTION
OF NITRATES AND NITRITES BY THE ELECTRON-RESERVOIR COMPLEXES [
FE ^-CSRLRX^-ARENE)] 784 4.6.3 MEDIATION BY FERROCENIUM CATION:
DERIVATIZED ELECTRODES 786 4.7 SENSORS 788 4.8 CONCLUSION 789 4.9
EXPERIMENTAL: SYNTHESES OF THE ELECTRON-RESERVOIR COMPLEXES [FE N (^ 5
-C 5 R5)(?7 6 -C 6 ME 6 )][PF 6 ], [FE V-C 5 R 5 )(?7 6 -C 6 ME 6 )],
AND [FE N V-C 5 R 5 )(?7 6 -C 6 ME 6 )][SBCL 6 ] 2 (R = H OR ME) 792
4.9.1 [FE N CP(?7 6 -C 6 ME 6 )][PF 6 ] 792 4.9.2 [FE I CP(J7 6 -C 6 ME
6 )] 792 4.9.3 [FEV-C 5 ME 5 )(;7 6 -C 6 ME 6 )] 793 4.9.4 [FE V-C 5 ME
5 )(;7 6 -C 6 ME 6 )][SBCL 6 ] 2 793 REFERENCES 793 5 ELECTRON-TRANSFER
PROCESSES IN MONONUCLEAR POLYPYRIDINE-TYPE METAL COMPLEXES* 804 ANTONIN
VLCEK, JR, AND J. HEYROVSKY 5.1 INTRODUCTION 804 5.2 ELECTRON-TRANSFER
PROPERTIES OF GROUND-STATE POLYPYRIDINE COMPLEXES: A SURVEY 807 5.2.1
THE 2,2 -BIPYRIDINE AND OTHER POLYPYRIDINE LIGANDS 807 5.2.2
POLYPYRIDINE COMPLEXES 809 5.3 ELECTRON-TRANSFER PROPERTIES OF
GROUND-STATE POLYPYRIDINE COMPLEXES: PHENOMENA 820 5.3.1 LOCALIZATION OF
REDOX STEPS 820 5.3.2 REDOX PATTERNS 823 5.3.3 CONTROL OF REDOX
POTENTIALS BY THE POLYPYRIDINE LIGAND STRUCTURE.. 828 5.3.4
ELECTRON-TRANSFER KINETICS 830 5.3.5 LIGAND LABILIZATION 833 5.3.6 REDOX
PROPERTIES OF SUPERMOLECULES CONTAINING METAL-POLYPYRIDINE UNITS 834 XXN
CONTENTS 5.3.7 APPLICATIONS OF GROUND-STATE ELECTRON TRANSFER 836 5.4
ELECTRON-TRANSFER PROPERTIES OF ELECTRONICALLY EXCITED POLYPYRIDINE
COMPLEXES 837 5.4.1 BASIC THERMODYNAMIC AND KINETIC ASPECTS OF
EXCITED-STATE ELECTRON TRANSFER 838 5.4.2 EXCITED STATES OF POLYPYRIDINE
COMPLEXES 840 5.4.3 CONTROL OF THE ELECTRON-TRANSFER PROPERTIES OF MLCT
EXCITED STATES OF POLYPYRIDINE COMPLEXES 842 5.4.4 PROPERTIES OF SOME
COMMON PHOTO-REDOX-ACTIVE METAL- POLYPYRIDINE CHROMOPHORES 846 5.4.5
BIMOLECULAR ELECTRON-TRANSFER REACTIONS 850 5.4.6 ULTRA-FAST ELECTRON
INJECTION TO SEMICONDUCTOR ELECTRODES 851 5.4.7 EXCITED-STATE
ELECTRON-TRANSFER IN SUPERMOLECULES CONTAINING METAL-POLYPYRIDINE
CHROMOPHORES 853 5.4.8 CHEMILUMINESCENCE 857 5.4.9 APPLICATIONS OF
PHOTOCHEMICAL ELECTRON TRANSFER 858 5.5 CONCLUSIONS 862 APPENDIX 864
REFERENCES 868 6 ELECTRON TRANSFER IN CATALYTIC DINITROGEN REDUCTION 878
ALEXANDER E. SHILOV 6.1 INTRODUCTION 878 6.2 PECULIARITIES OF THE N 2
MOLECULE 879 6.3 DINITROGEN COMPLEXES WITH TRANSITION METALS: POSSIBLE
CATALYSTS FOR N 2 REDUCTION 882 6.4 MONONUCLEAR COMPLEXES M-N=N 883 6.5
LINEAR DINUCLEAR COMPLEXES M-N=N-M 883 6.6 POLYNUCLEAR DINITROGEN
COMPLEXES 884 6.7 POLYNUCLEAR COMPLEX AS OPTIMUM CATALYST FOR N 2
REDUCTION 885 6.8 ELECTRON TRANSFER IN BIOLOGICAL NITROGEN FIXATION 886
6.9 N 2 REDUCTION IN APROTIC MEDIA 891 6.10 DINITROGEN REDUCTION IN
PROTIC MEDIA 892 6.11 SOLUBLE COMPLEXES OF VANADIUM (II) 894 6.12
CATALYTIC DINITROGEN REDUCTION 897 6.13 CATALYTIC DINITROGEN REDUCTION
BY AMALGAMS 899 6.14 FEMOCO AS CATALYST FOR THE REDUCTION OF NITROGENASE
SUBSTRATES AT AMALGAM SURFACES 901 REFERENCES 903 7 TRANSITION-METAL
COMPLEXES AS MODELS OF THE ACTIVE SITES OF HYDROGENASES* 905 CAMERON E.
FORDE AND ROBERT H. MORRIS 7.1 HYDROGEN CHEMISTRY 905 7.1.1 INTRODUCTION
905 7.1.2 METAL HYDRIDE CHEMISTRY 906 CONTENTS XXIN 7.1.3 METAL
DIHYDROGEN CHEMISTRY 906 7.2 HYDROGENASE ENZYMES 909 7.2.1 INTRODUCTION
TO HYDROGENASE ENZYMES 909 7.2.2 SPECTROSCOPIC CHARACTERIZATION OF
HYDROGENASE ENZYMES 910 7.2.3 HYDROGENASE FUNCTION 915 7.2.4 STRUCTURAL
CHARACTERIZATION OF HYDROGENASE ENZYMES 915 7.3 MODELING WITH
TRANSITION-METAL COMPLEXES 916 7.3.1 INTRODUCTION 916 7.3.2
SPECTROSCOPIC MODELING 917 7.3.3 FUNCTIONAL MODELING 918 7.3.4
STRUCTURAL MODELING 920 7.3.5 THEORETICAL MODELING 921 7.4 CONCLUSIONS
923 REFERENCES 924 8 BIOMIMETIC ELECTRON-TRANSFER CHEMISTRY OF
PORPHYRINS AND METALLOPORPHYRINS 927 SHUNICHI FUKUZUMI AND HIROSHI
IMAHORI 8.1 INTRODUCTION 927 8.2 HIGH-VALENT INTERMEDIATES OF HERNE
ENZYMES 928 8.2.1 P-450 CATALYTIC MECHANISMS 928 8.2.2 REACTION PATHWAYS
OF [(P)FE IV =0]-+ 930 8.2.3 REORGANIZATION ENERGIES FOR
ELECTRON-TRANSFER REACTIONS OF HIGH-VALENT IRON PORPHYRINS 933 8.2.4
ELECTRON-TRANSFER PATHWAY OF [(P)FE TV =0]-+ 934 8.2.5 ELECTRON TRANSFER
COMPARED WITH DIRECT OXYGEN TRANSFER 938 8.2.6 AGOSTIC INTERACTION 941
8.2.7 SITE OF ELECTRON TRANSFER IN COMPOUND I 943 8.2.8 PHOTOINDUCED
ELECTRON-TRANSFER OXIDATION 944 8.2.9 OXYGEN-EVOLVING COMPLEX 947 8.3
CATALYTIC REDUCTION OF OXYGEN 949 8.3.1 TWO-ELECTRON REDUCTION 950 8.3.2
FOUR-ELECTRON REDUCTION 952 8.4 ELECTRON TRANSFER IN ORGANIZED MEDIA 954
8.4.1 ELECTROCATALYSIS OF SELF-ASSEMBLED MONOLAYERS OF PORPHYRINS 955
8.4.3 PHOTOINDUCED ELECTRON TRANSFER OF METALLOPORPHYRINS IN SELF-
ASSEMBLED MONOLAYERS 957 8.4.4 SELF-ASSEMBLED MONOLAYERS OF
PORPHYRIN-CONTAINING DYADS 960 8.4.5 SELF-ASSEMBLED MONOLAYERS OF
PORPHYRIN-CONTAINING TRIADS 963 8.5 SUMMARY 965 ACKNOWLEDGMENT 966
REFERENCES 966 9 ESR SPECTROSCOPY OF INORGANIC AND ORGANOMETALLIC
RADICALS 976 WOLFGANG KAIM 9.1 INTRODUCTION: THE INFORMATION ACCESSIBLE
FROM ESR 976 XXIV CONTENTS 9.2 INORGANIC AND ORGANOMETALLIC RADICALS:
DEFINITION, GENERATION AND PECULIARITIES 976 9.3 SELECTED ESR PARAMETERS
979 9.3.1 CONCENTRATION AND LIFETIME OF RADICALS 979 9.3.2 LINE-WIDTH
AND TEMPERATURE 980 9.3.3 THE G FACTOR 981 9.3.4 ELECTRON-NUCLEAR
HYPERFINE COUPLING 985 9.3.5 ZERO-FIELD SPLITTING AND EXCHANGE COUPLING
991 9.3.6 DYNAMIC EFFECTS 991 9.3.7 ESR INFORMATION AND CHEMICAL
REACTIVITY 996 9.3.8 CONCLUDING REMARKS 998 ACKNOWLEDGMENTS 998
REFERENCES 998
|
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| id | DE-604.BV013463658 |
| illustrated | Illustrated |
| indexdate | 2024-07-09T18:46:19Z |
| institution | BVB |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-009188970 |
| oclc_num | 48487199 |
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| owner_facet | DE-29T DE-703 DE-384 DE-20 DE-19 DE-BY-UBM DE-355 DE-BY-UBR DE-11 |
| physical | XLVII, 1002 S. Ill., graph. Darst. |
| publishDate | 2001 |
| publishDateSearch | 2001 |
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| publisher | Wiley-VCH |
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| spelling | Electron transfer in chemistry 2 Organic molecules, organometallic and inorganic molecules Vincenzo Balzani (ed.) Weinheim [u.a.] Wiley-VCH 2001 XLVII, 1002 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Oxidation-reduction reaction Balzani, Vincenzo 1936- Sonstige (DE-588)10907811X oth (DE-604)BV013463647 2 GBV Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=009188970&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Electron transfer in chemistry Oxidation-reduction reaction |
| title | Electron transfer in chemistry |
| title_auth | Electron transfer in chemistry |
| title_exact_search | Electron transfer in chemistry |
| title_full | Electron transfer in chemistry 2 Organic molecules, organometallic and inorganic molecules Vincenzo Balzani (ed.) |
| title_fullStr | Electron transfer in chemistry 2 Organic molecules, organometallic and inorganic molecules Vincenzo Balzani (ed.) |
| title_full_unstemmed | Electron transfer in chemistry 2 Organic molecules, organometallic and inorganic molecules Vincenzo Balzani (ed.) |
| title_short | Electron transfer in chemistry |
| title_sort | electron transfer in chemistry organic molecules organometallic and inorganic molecules |
| topic | Oxidation-reduction reaction |
| topic_facet | Oxidation-reduction reaction |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=009188970&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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