Ligands polarization

Mason SF (1980) The Ligand Polarization Model for the Spectra of Metal Complexes. The Dynamic Coupling Transition Probabilities. 39 43-81 Massey V, see Hemmerich P (1982) 48 93-124... 

In applying these ideas, polarizing power and polarizability must be interpreted in terms of the electronic structures of the central metal and the ligands. Polarizing power is not simply a function of z/r [thus note that the ionizing po-. 

Ligand Polarization. Polarization is the most important immediate consequence of ligand coordination. The fact that ligand polarization can assist some of the ligand reactions was first expounded in detail and used by Meerwein 14, 24), Meerwein also provided (but never published) the first interpretation of the way in which coordination may affect the path of the activated complex along the reaction coordinate. Fairly comprehensive reviews of this type of reaction are available 11, 18), However, the kinetic aspects have rarely been discussed in detail (except for biochemical cases 23, 8)), because comparative experimental data are meager. Therefore, the examples cited below fall into several loosely related groups. 

The information available on aliphatic systems is much more diversified than that on aromatic systems though the effects of ligand polarization are similar. In general, metal ions allow us to generate the ligand polarization which assists nucleophilic attack. For suitable ligands this can be effected in a basic environment where protons cannot furnish the same general effect. 

For isotropic ligand subsystems, the a-th vector component of the ligand polarization contribution to the total transition dipole moment may be written as ... 

In contrast to the somewhat more complicated ligand polarization model and some other related theoretical approaches that are applicable by a limited number of specialists, the simple analysis provided in a black box manner by DFT is expected to afford a new reliable tool on a semiquantitative basis for the future determination of absolute configurations of inorganic complexes even for nonspecialists. 

The observed ft . are minimized root mean square values based upon the spectroscopic data reported by Ciampolini et al. [66]. The individual crystal field contributions ft .(CF) are listed for each calculated ft together with the particular ligand polarization contribution ft (LP). The calculated total ft .(tot) sums the crystal field (CF) and ligand field (LF) contributions with the CF-LP cross-term. 

Mason, S. F. The Ligand Polarization Model for Ae Spectra of Metal Complexes The Dynamic Coupling Transition Probabihties. Vol. 39, pp. 43-81. 

Dynamic Metal-Ligand Coupling the Ligand Polarization Model.50... 

The Ligand Polarization Model for the Spectra of Metal Complexes... 

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