Coordination compounds Homogeneous catalysis Ligands, Metal

The manifold intermediates in homogeneous transition-metal catalysis are certainly metal complexes and therefore show a behaviour like ordinary coordination compounds associations of phosphorus donors open up multifarious additional controls. Both, substrates and P ligands are Lewis bases that we have to consider and that compete at the coordination centers of the metal, leading to competitive, non-competitive or uncompetitive activation or inhibition processes in analogy to the terminology of enzyme chemistry... 

Of particular interest as catalysts are the incompletely coordinated metal chelate compounds, which are sufficiently stabilized by the ligand to be stable in solution at pH values much higher than that at which the aquo metal ion would precipitate as the hydroxide and thus to become unavailable for homogeneous catalysis. Such a metal chelate would be particularly effective as a catalyst for the activation of a substrate which can coordinate to the metal ion in the chelate compound. The interaction of the substrate with the metal ion would increase its reactivity toward nucleophilic reagents such as solvent molecules or hydroxyl ions, in accordance with the following scheme ... 

Spectrophotometry. The theory of spectra is far advanced. In many cases, compounds can be unambiguously identified by their ultraviolet, visible, or infrared spectra (e.g., see Smith s book [43]). As an example, the double bond of a CO ligand in a complex has a strong characteristic infrared vibration frequency whose exact value depends on the electronic properties of the coordinating metal these, in turn, are affected by the other substituents. In homogeneous catalysis by transition-metal complexes in particular, foremost among them hydrogenation, hydroformylation, and hydrocyanation, spectra have contributed much to the identification of reaction intermediates and thus of pathways. 

Asymmetric catalysis is one of the most economical processes for the production of chiral compounds, considering the high turnover levels of most homogeneous catalysts and the fact that the optically active catalyst introduces its chiral information during each new catalytic cycle. The asymmetric catalyst molecules are mainly synthesized by coordination of optically active ligands to a metal rather than resolution of complexes in which the optical activity lies at the metal, and which are prone to racemization. These chiral complexes involve only a few metals. 

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