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 Rotation 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.