Metal Vinylidenes and Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis

Focusing on preparation and applications in synthesis and catalysis, this book finally closes a gap in the literature by summarizing this hot topic for the first time.
As such, it gathers in one volume the key features of metal vinylidene and allenylidene complexes as well as reactive species and covers applications in metathesis, polymerization, molecular materials, carbon rich compounds and fine chemical production. The emphasis here is on the selective transformations of alkynes and enynes plus simple and complex molecules containing a triple C–C bond.
The result is a must–have ready reference for organic, catalytic, complex, theoretical and polymer chemists, as well as those working with/on organometallics.


Spis treści:
Preface.
List of Contributors.
1. Preparation and Stoichiometric Reactivity of Mononuclear Metal Vinylidene Complexes (Michael I. Bruce).
1.1. Introduction.
1.2. Preparative Methods.
1.3. Stoichiometric Reactions.
1.4. Chemistry of Specific Complexes.
1.5. Reactions Supposed to Proceed via Metal Vinylidene Complexes.
2. Preparation and Stoichiometric Reactivity of Metal Allenylidene Complexes (Victorio Cadierno, Pascale Crochet, and José Gimeno).
2.1. Introduction.
2.2. Preparation of Allenylidene Complexes.
2.3. Coordination Modes and Structural Features.
2.4. Stoichiometric Reactivity of Allenylidenes.
2.5. Concluding Remarks.
3. Preparation and Reactivity of Higher Metal Cumulenes Longer than Allenylidenes (Helmut Fischer).
3.1. Introduction.
3.2. Steric and Electronic Structure.
3.3. Synthesis of Cumulenylidene Complexes.
3.4. Reactions of Higher Metal Cumulenes.
3.5. Summary and Conclusion.
4. Theoretical Aspects of Metal Vinylidene Allenylidene Complexes (Jun Zhu and Zhenyang Lin).
4.1. Introduction.
4.2. Electronic Structures of Metal Vinylidene and Allenylidene Complexes.
4.3. Barrier of R otation Of Vinylidene Ligands.
4.4. Tautomerization Between ŋ2 –Acetylene and Vinylidene on Transition Metal Centers.
4.5. Reversible C–C σ–bond Formation by Dimerization of Metal Vinylidene Complexes.
4.6. Metal Vinylidene Mediated Reactions.
4.7. Heavier Group 14 Analogs of Metal Vinylidene Complexes.
4.8. Allenylidene Complexes.
4.9. Summary.
5. Group 6 Metal Vinylidenes in Catalysis (Cr, Mo, W) (Nobuharu Iwasawa).
5.1. Introduction.
5.2. Preparation of Fischer–type Carbene Complexes through the Generation of the Vinylidene Complexes.
5.3. Utilization of Pentacarbonyl Vinylidene Complexes of Group 6 Metals for Synthetic Reactions.
5.4. Utilization of Vinylidene to Alkyne Conversion.
5.5. Synthetic Reactions Utilizing Other Kinds of Vinylidene Complexes of Group 6 Metals.
5.6. Conclusion.
6. Ruthenium Vinylidenes in the Catalysis of Carbocyclization (Arjan Odedra and Rai–Shung Liu).
6.1. Introduction.
6.2. Stoichiometric Carbocyclization via Ruthenium Vinylidene.
6.3. Catalytic Carbocyclization via Electrocyclization of Ruthenium–Vinylidene Intermediates.
6.4. Catalytic Carbocyclization via Cycloaddition of Ruthenium Vinylidene Intermediates.
6.5. Catalyzed Cyclization of Alkynals to Cycloalkenes.
6.6. Ruthenium–Catalyzed Hydrative Cyclization of 1,5–Enynes.
6.7. Carbocyclization Initiated by Addition of C–Nucleophile to Ruthenium Vinylidene.
6.8. Conclusion.
7. Allenylidene Complexes in Catalysis (Yoshiaki Nishibayashi and Sakae Uemura).
7.1. Introduction.
7.2. Propargylic Substitution Reactions.
7.3. Propargylation of Aromatic Compounds with Propargylic Alcohols.
7.4. Carbon–Carbon Bond Formation via Allenylidene–Ene Reactions.
7.5. Reductive Coupling Reaction via Hydroboration of Allenylidene Intermediates.
7.6. Selective Preparation of Conjugated Enynes.
7.7. Preparation of Dicationic Chalcogenolate–Bridged Diruthenium Complexes and Their Dual Catalytic Activity.
7.8. Other Catalytic Reactions via Allenylidene Complexes as Key Intermediates.
7.9. Conclusion.
8. Ruthenium Allenylidenes and Idenylidenes as Catalysts in Alkene Metathesis (Raluca Malacea and Pierre H. Dixneuf).
8.1. Introduction.
8.2. Propargyl Derivatives as Alkene Metathesis Initiator Precursors: Allenylidenes, Indenylidenes and Alkenylalkylidenes.
8.3. Indenylidene–Ruthenium Catalysts in Alkene Metathesis.
8.4. Conclusion.
9. Rhodium and Group 9–11 Metal Vinylidenes in Catalysis (Sean H. Wiedemann and Chulbom Lee).
9.1. Introduction.
9.2. Rhodium and Iridium Vinylidenes in Catalysis.
9.3. Rhodium Alkenylidenes in Catalysis.
9.4. Group 10 and 11 Metal Vinylidenes in Catalysis.
9.5. Conclusion.
9.6. Note Added in Proof.
10. Anti–Markovnikov Additions of O–, N–, P–Nucleophiles to Triple Bonds with Ruthenium Catalysts (Christian Bruneau).
10.1. Introduction.
10.2. Co–O Bond Formation.
10.3. Formation of C–N Bonds via Anti Markovnikov Addition to Terminal Alkynes.
10.4. Hydrophosphination: Synthesis of Vinylic Phosphine.
10.5. C–C Bond Formation: Dimerization of Terminal Alkynes.
Index.

Nota biograficzna:
Pierre H. Dixneuf, professor at the University of Rennes has been the head of the CNRS research Unit 6509 in Rennes (1986–1999), and he created the Institute of Chemistry in Rennes in 2000. He was research advisor at the University of Rennes (2001–04) and at CNRS chemistry headquarters (1996–99).
He obtained his academic degrees, PhD and habilitation, in Rennes was on leave of absence with professor M. F. Lappert, University of Sussex for one year. He innovated first in organometallic chemistry and then in homogeneous catalysis and conjugated carbon–rich systems. He ha s authored over 330 publications of which 70 in the last 5 years.
He has received several research awards : Le Bel (SFC), Grignard–Wittig (GDCh), Sacconi (Italy 2006), Académie des Sciences grand prix (2006).
Dr. Christian Bruneau is the head of the CNRS–University research group "Catalysis and Organometallics" in Rennes. He graduated in Chemistry from the Institut National Supérieur de Chimie Industrielle de Rouen in 1974, and obtained his Doctorate degree at the ENSCR national school of Rennes. Since 1986, he has been developing his research activities in the field of molecular organometallic catalysis. He is strongly involved in ruthenium–catalyzed selective transformations of alkynes, alkenes and enynes, cycloisomerization, rearrangement, and addition reactions. He is developing a topic on enantioselective reactions, mainly hydrogenation and allylic substitution with transition metal catalysts.

Okładka tylna:
Focusing on preparation and applications in synthesis and catalysis, this book finally closes a gap in the literature by summarizing this hot topic for the first time.
As such, it gathers in one volume the key features of metal vinylidene and allenylidene complexes as well as reactive species and covers applications in metathesis, polymerization, molecular materials, carbon rich compounds and fine chemical production. The emphasis here is on the selective transformations of alkynes and enynes plus simple and complex molecules containing a triple C–C bond.
The result is a must–have ready reference for organic, catalytic, complex, theoretical and polymer chemists, as well as those working with/on organometallics.