金属有机化学第十一章.pptVIP

* Bonding in Carbenes There are two limiting classes of carbenes: electrophilic (Fischer) carbenes and nucleophilic (Schrock) carbenes. Chapter 11 Carbenes, Carbynes, and metallacycles Schrock carbenes ? High oxidation state, early transition metals ? non-π-acceptor ligands on M ? non-π-donor substituents (R) on the carbene Schrock carbenes are formally considered as X2-type ligands derived from triplet carbenes. The carbene carbon has a partial negative charge and acts as a nucleophile. Fischer carbenes ? Low oxidation state, late transition metals ? π-acceptor ligands on M ? π-donor substituents (R) on the carbene Fischer carbenes can be considered as neutral 2 e ligands (L-type) derived from singlet carbenes. Since the carbene is acting as a ?-donor, it has a ?+ charge and acts as an electrophilic center. Fischer Carbenes E. O. Fischer first reported carbene complexes in 1964. (Angew. Chem. Int. Ed., 1964, 3, 580) Preparation A. Nucleophilic attack on coordinated ligand B. From acetylides (Chugaev, J. Russ. Chem. Soc., 1915, 47, 776; Inorg. Chem. , 1971, 10, 1711) C. From stable carbenes (Angew. Chem. Int. Ed. 1997, 36, 2162-2187; J. Organomet. Chem., 2000, 600, 12-22) Stable carbenes developed by Arduengo (Acc. Chem. Res. 1999, 32, 913) can be used as neutral 2e ligands in place of CO or phosphines. The carbene can either be preformed or prepared in situ. Electrophilic Reactivity Much of the reactivity of Fischer carbenes is directly analogous to the reactivity of carboxylic acid derivatives. Both have electrophilic carbon centers with leaving groups. A. Nucleophilic attack B. “Enolate” reactivity Schrock Carbenes Synthesis The first nucleophilic carbenes were prepared by Schrock in an effort to prepare a homoleptic tantalum(V) alkyl. (Acc. Chem. Res., 1979, 12, 98) Sterically crowded early transition metal alkyls undergo ?-elimination readily to give nucleophilic carbenes and alkanes. Carbene formation can be promoted by increa