金属有机化学：8-homo-2.ppt

Homogeneous catalysis MT Organometallics Organometallic compounds of the transition metals have unusual structures, and practical applications in organic synthesis and industrial catalysis. MT Organometallics One of the earliest compounds, known as Zeise’s salt, was prepared in 1827. It contains an ethylene molecule π bonded to platinum (II). Zeise’s Salt The bonding orbital of ethene donates electrons to the metal. The filled d orbitals (dxz or dyz) donate electrons to the antibonding orbital of ethene. Square Planar Complexes The complexes of platinum(II), palladium(II), rhodium(I) and iridium(I) usually have 4-coordinate square planar geometry. These complexes also typically contain 16 electrons, rather than 18. The stability of 16 electron complexes, especially with σ-donor π-acceptor ligands, can be understood by examining a MO diagram. Square Planar Complexes The electron pairs from the 4 ligands used in σ bonding occupy the bonding orbitals. Square Planar Complexes The dxy, dxz, dyz and dz2 orbitals are either weakly bonding, non-bonding, or weakly antibonding. Square Planar Complexes The dx2-y2 orbital is anti-bonding, and if filled, will weaken the σ bonds with the ligands. Square Planar Complexes As a result, 16 electrons will produce a stable complex. Catalysis of Square Planar Compounds Square planar complexes are often involved as catalysis for reactions. The four-coordinate complexes can undergo addition of organic molecules or hydrogen, and then be regenerated as the organic product is released from coordination to the catalyst. Catalysis – aldehyde formation Pd(II) undergoes addition of an alkene which is subsequently converted to an alcohol. Addition of a hydrogen atom to the metal with subsequent migration to the alcohol produces an aldehyde. Hydrogenation Hydrocarbons can bond to transition metals via σ bonds or π bonds. Wilkinson’s catalyst, [RhCl(PPh3)] is used to hydrogenate a wide variety of alkenes using pressures of