Organometallic Chemistry (eBook)

Plenary Lectures Presented at the Eighth International Conference on Organometallic Chemistry, Kyoto, Japan, 12-16 September 1977

N. Hagihara, Y. Ishii (Herausgeber)

eBook Download: PDF

2017 | 1. Auflage
135 Seiten
Elsevier Science (Verlag)
978-1-4831-5378-0 (ISBN)

Infos

Organometallic Chemistry - 8 focuses on the compositions, reactions, properties, and transformations of molecules, silicon carbon, molybdenum and tungsten compounds, palladium, and platinum. The selection first offers information on the theoretical aspects of the coordination of molecules to transition metal centers and generation and reactions of silicon-carbon double-bonded intermediates. Discussions focus on photolysis of naphthyldisilanes, alkenyldisilanes, phenylacetylene, and benzenoid aromatic derivatives of disilane. The book also considers classical and novel ylide systems in organometallic chemistry, including phosphorinanium and phospholanium ylides and organometallic compounds of double ylides. The text evaluates studies on the synthesis, mechanism, and reactivity of organo-molybdenum and tungsten compounds and enantioselective reactions through chiral metal-carbene intermediates. The manuscript also ponders on the synthesis and reactivity of carbon-bonded transition elements; neutron diffraction studies on transition metal hydride complexes; and applications of palladium in organic syntheses. The selection is an impressive reference for readers and chemists interested in organometallic chemistry.

Inhalt

Front Cover 1
Organometallic Chemistry — 8 4
Copyright Page 5
Table of Contents 6
CHAPTER 1. THEORETICAL ASPECTS OF THE COORDINATION OF MOLECULES TO TRANSITION METAL CENTERS 8
Abstract 8
THE FRAGMENT AND SUBSTITUTIONAL APPROACHES. A CASE STUDY OF Fe(CO)4 (ETHYLENE). 9
ROTATIONAL BARRIERS IN POLYENE AND CYCLOPOLYENE-ML3 COMPLEXES 11
Acknowledgment 15
REFERENCES 16
CHAPTER 2. PHOTOLYSIS OF ORGANOPOLYSILANES. GENERATION AND REACTIONS OF SILICON CARBON DOUBLE-BONDED INTERMEDIATES 18
Abstract 18
INTRODUCTION 18
PHOTOLYSIS OF BENZENOID AROMATIC DERIVATIVES OF DISILANE 18
PHOTOLYSIS OF NAPHTHYLDISILANES 22
PHOTOLYSIS OF ALKENYLDISILANES 22
PHOTOLYSIS OF (PENTAMETHYLDISILANYL) PHENYLACETYLENE 24
Acknowledgment 25
REFERENCES 25
CHAPTER 3. CLASSICAL AND NOVEL YLIDE SYSTEMS IN ORGANOMETALLIC CHEMISTRY 26
Abstract 26
INTRODUCTION 26
Tert.-butvl-methylene-phosphoranes 27
Phosphorinanium and Phospholanium Ylides 28
Organometallic Compounds of Double Ylides 29
Phosphonium-bis-methylide/Bis-phosphino-methanide Complexes 30
REFERENCES 31
CHAPTER 4. STUDIES ON SYNTHESIS, MECHANISM AND REACTIVITY OF SOME ORGANO–MOLYBDENUM AND –TUNGSTEN COMPOUNDS 34
ABSTRACT 34
I. THE ACTIVATION OF C–H BONDS BY .–CYCLOPENTADIENYL–TUNGSTEN DERIVATIVES. 34
II. EVIDENCE FOR THE REVERSIBLE a-ELIMlNATION OF HYDROGEN FROM A TUNGSTENMETHYL COMPOUND 38
III. METALLOCYCLOBUTANE DERIVATIVES OF MOLYBDENUM AND TUNGSTEN. 39
IV. RULES FOR PREDICTING THE REGIOSELECTIVITY OF NUCLEOPHILIC ADDITION ON 18–ELECTRON ORGANOTRANSITION METAL CATIONS CONTAINING POLYENE LIGANDS. 41
ACKNOWLEDGEMENTS 42
REFERENCES 42
CHAPTER 5. ENANTIOSELECTIVE REACTIONS THROUGH CHIRAL METAL-CARBENE INTERMEDIATES 44
Abstract 44
INTRODUCTION 44
RESULTS 45
CONCLUDING REMARKS 49
Acknowledgment 49
REFERENCES 49
CHAPTER 6. ISOCYANIDE, CARBENE, AND RELATED CHEMISTRY OF PALLADIUM(II) AND PLATINUM(II) 50
Abstract 50
INTRODUCTION 50
RESULTS AND DISCUSSION 50
Acknowledgement 54
REFERENCES 54
CHAPTER 7. SYNTHESIS AND REACTIVITY OF CARBON-BONDED TRANSITION ELEMENTS 56
Abstract 56
A) Reactions of Coordinated CO 56
B) Reactions of CO2 and CO2-Like Molecules with Compounds of Transition Elements 58
C) Coordinative Addition of CO and Olefins 59
D) Reactivity of Anhydrous Gold (III) Chloride 59
E) Organic Dichalcqgenides as Bridging Ligands for Rhenium (I) Carbonyl Compounds 59
Acknowledgement 59
REFERENCES 60
CHAPTER 8. NEUTRON DIFFRACTION STUDIES ON TRANSITION METAL HYDRIDE COMPLEXES 62
Abstract 62
INTRODUCTION 62
TERMINAL METAL-HYDROGEN (M–H) BONDS 63
BRIDGING METAL–HYDROGEN (M–H–M) BONDS 65
TRIPLY-BRIDGING METAL-HYDROGEN [(µ3 -H)M3] BONDS 68
Acknowledgements 70
REFERENCES 70
CHAPTER 9. ORGANO TRANSITION METAL COMPOUNDS AS INTERMEDIATES IN HOMOGENEOUS CATALYTIC REACTIONS 72
Abstract 72
INTRODUCTION 72
REFERENCES 84
CHAPTER 10. NEW APPLICATIONS OF PALLADIUM IN ORGANIC SYNTHESES 86
Abstract 86
Acknowledgment 96
CHAPTER 11. UNUSUAL METAL ALKYLS 98
Abstract 98
INTRODUCTION AND INITIAL OBJECTIVES 98
NEW RESULTS 98
Acknowledgement 102
REFERENCES 102
CHAPTER 12. STOICHIOMETRIC VERSUS CATALYTIC USE OF COPPER(I) SALTS IN THE SYNTHETIC USE OF MAIN GROUP ORGANOMETALLICS 104
Abstract 104
INTRODUCTION 104
I ADDITION TO UNSATURATED C=C BONDS 104
II ALKYLATION BY SUBSTITUTION REACTIONS 107
Acknowledgments 110
REFERENCES 110
CHAPTER 13. ON THE MECHANISMS OP SUBSTITUTION REACTIONS OF ORGANOMETALLIC COMPOUNDS OP NONTRANSITION METALS 112
Abstract 112
REFERENCES 118
CHAPTER 14. ACTIVATION OP ALKANES BY TRANSITION METAL COMPLEXES 120
Abstract 120
INTRODUCTION 120
H-D EXCHANGE 121
OTHER CATALYTIC REACTIONS OF ALKANES 122
MECHANISM Of ALKANES ACTIVATION 123
REFERENCES 128
CHAPTER 15. NEW TRENDS IN THE CHEMISTRY OF ORGANOMETALLOPORPHYRINS 130
Abstract 130
ACKNOWLEDGEMENT 136
REFERENCES 136

Produkt-Details

• Erscheint lt. Verlag: 31.1.2017
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Technik
• ISBN-10: 1-4831-5378-9 / 1483153789
• ISBN-13: 978-1-4831-5378-0 / 9781483153780