Reactions of organometallic complexes

Reaction of Organometallic Complexes with Oxide Supports ... 

Reaction of Organometallic Complexes with Particles of Transition Elements The Stepwise Hydrogenolysis of Metal-Carbon Bonds... 

The synthesis, characterization, and catalytic properties of materials obtained by the reaction of organometallic complexes of IIB, IVA, and VIA with metallic particles were studied extensively. Two types of materials may be obtained by... 

Catalysts are heterogeneous sulfided nickel (or cobalt) molybdenum compounds on a y-alumina. The reaction has been extensively studied with substrates such as thiophene (Figure 2.40) as the model compound mainly with the aims of improving the catalyst performance. The mechanism on the molecular level has not been established. In recent years the reaction has also attracted the interest of organometallic chemists who have tried to contribute to the mechanism by studying the reactions of organometallic complexes with thiophene [41], Many possible co-ordination modes for thiophene have been described. 

For group Vlll metal surfaces, the reaction of organometallic complexes can... 

The Organometallic Chemistry of the Transition Metals, R. H. Crabtree, Wiley-Interscience 2005 (4th edn.), 546 pp., ISBN 0-471-66256-9. This is the best graduate-level textbook in organometallic chemistry. It is clear and well written, covering all of the fundamental reactions of organometallic complexes, plus some applications. Each chapter also contains exercises and up-to-date references. 

Lees AJ, Purwoko AA. Photochemical mechanisms in intermolecular C-H bond activation reactions of organometallic complexes. Coord Chem Rev 1994 132 155-160. 

Peripheral reactions of organometallic complexes with phosphaalkynes give access to a variety of four-membered organophosphor ring ligands. 

Our understanding of organic reactions catalyzed by soluble metal complexes ( homogeneous catalysis ) is based on the properties and stoichiometric reactions of organometallic complexes, defined as molecules containing metal-carbon bonds. Significant aspects are summarized below, but for details the reader is recommended to one of the excellent texts cited at the end of this Appendix. 

Very often, amine complexes are designed to illustrate some subtle mechanistic see Mechanisms of Reaction of Organometallic Complexes) or stereochemical effect in coordination chemistry and much effort has been exercised in the design of specific amine ligands. For example, the reaction shown in equation (7) is very sensitive to steric effects, and the introduction of a pyridine ligand in place of an... 

Under lower CO partial pressures a 16e RCo(CO)3 species will have a long enough lifetime to allow reverse P-Hydride Elimination (see Mechanisms of Reaction of Organometallic Complexes) and increase the possibility for alkene reinsertion to the branched alkyl species, which is slightly more favored thermodynamically. At this point, CO addition and insertion will yield a branched aldehyde, or another /3-hydride elimination can give alkene isomerization. This second mechanistic explanation is in line with more recent results from Rh/PPh3-catalyzed hydroformylation studies (see Section 2.4). 

Bonding Energetics of Organometallic Compounds Cobalt Inorgatuc Coordination Chemistry Cobalt Organometallic Chemistry Mechanisms of Reaction of Organometallic Complexes. 

Insertion of CO into RCo(CO)4 to give acyl complexes is facile (see Mechanisms of Reaction of Organometallic Complexes). This reaction proceeds at 1 atm of CO at ambient temperature. The alkyl-acyl equilibrium lies far towards the acyl complex. The activation energy for the process has been calculated by MO methods to be about 85 kJmol (see Molecular Orbital Theory). Thus, RCo(CO)4 complexes can only be obtained under conditions of low CO pressure, which in turn opens the way for CO dissociative decomposition. Cobalt acyl complexes can be derivatized in several ways to form various products (Scheme 5). 

The most conunon organogold(I) compounds of the type L AuR can undergo ligand exchange of L, which is known to follow an associative mechanism (equation 39) (see Mechanisms of Reaction of Organometallic Complexes). 

Asymmetric Synthesis by Homogeneous Catalysis Coordination Organometallic Chemistry Principles Hydrobo-ration Catalysis Hydrogenation Isomerization of Alkenes Mechanisms of Reaction of Organometallic Complexes Silicon Organosilicon Chemistry. 

In transition metal-main group element clusters, there is the possibility of ligand substitution at either type of element center. Displacement of an exo-cluster ligand on one of the metal centers (equation 10) is to be expected (see Mechanisms of Reaction of Organometallic Complexes) However, displacement at a main group cluster site has also been observed (equation 11 ). Indeed, phosphine substitution takes place exclusively at the boron atom, and the osmium-substituted BCO complex can only be prepared by synthesizing it from the phosphine-substituted osmium carbonyl starting material. 

Carbonyl Complexes of the Transition Metals Mechanisms of Reaction of Organometallic Complexes Osmium Inorganic Coordination Chemistry Semiconductor Interfaces. 

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