Transition metals Jahn-Teller effects

Stable Mn(HI) compounds, Mn(R2r fc)3, have been known for a long time (42, 46). The structure of Mn(Et2C tc)3 is elucidated (47). The inner geometry of the Mn(CS2)3 core does not conform to the usual D3 point symmetry of transition metal complexes of this type, but shows a strong distortion attributed to the Jahn-Teller effect. The electronic spectrum (48, 49) and the magnetic properties of this type of complexes are well studied (50). 

Labile species are usually main group metal ions with the exception of Cr2+ and Cu2+, whose lability can be ascribed to Jahn-Teller effects. Transition metals of classes II and III are species with small ligand field stabilization energies, whereas the inert species have high ligand field stabilization energies (LFSE). Examples include Cr3+ (3d3) and Co3+ (3d6). Jahn-Teller effects and LFSE are discussed in Section 1.6. Table 1.9 reports rate constant values for some aqueous solvent exchange reactions.8... 

In geochemistry, the Jahn-Teller effect is relevant for metals Fe and in octahedral complexes and for Cr + and Ni in tetrahedral complexes. Other transition ions (e.g., Cr and Co ) require unusual oxidation or low-spin conditions that can be reached only under extreme pressure. 

A group of 8 ternary fluorides containing the transition metal ions Cr2+ and Cu + crystallizes in a tetragonedly distorted perovskite lattice. This distortion is caused by the Jahn-Teller effect displayed by the configurations d% d (Cr +) and d d (Cu2+) resp., rather than by geometrical reasons. As for their space requirements the ions Cr + and Cu + are very close in size to Mn2+ and Co + resp. and as a consequence the corresponding compounds do not differ in their tolerance factors. 

Jahn, H. A. Teller, E. Proc. Roy. Soc. bond. A 1937, 161, 220-235. Mckinlay, R. G. Paterson, M. J. The Jahn-Teller Effect in Binary Transition Metal Carbonyl Complexes. In The Jahn-Teller Effect Fundametals and Implications for Physics and Chemistry , Eds. Koppel, H. Yarkony,... 

Two additional factors that can contribute to line breadth and shape are spin-orbil coupling, which is particularly prevalent in complexes of the heavier transition metals, and departures from cubic symmetry, such as through the Jahn-Teller effect. This latter effect, which will be discussed later in this chapter, is believed to be responsible for the low-frequency shoulder observed on the absorption line for [TKH30)6)2 (Fig. 11.8). 

An example of the conflict between stabilization from the Jahn-Teller effect and chelate geometrical requirements is found in the ethylenediamme complexes of Cu2+. Most divalent transition metal ions form complexes with elhylencdiaminc (en) by stepwise replacement of water ... 

We discuss here two examples of vibronic effects in polynuclear highly symmetrical transition metal clusters. The existence of degenerate and quasi-degenerate molecular orbitals in their energy spectra results in the Jahn-Teller effect or in the vibronic mixing of different electronic states. We show that both quantum-chemical methods and model approaches can provide valuable information about these vibronic effects. In the case of the hexanuclear rhenium tri-anion, the Jahn-Teller effect is responsible for the experimentally observed tetragonal distortion of the cluster. The vibronic model of mixed-valence compounds allows to explain the nature of a transient in the photo-catalytic reaction of the decatungstate cluster. 

The spectacular relationship between the nature of the X3 species and the promotion energy shows that the VBSCD is in fact a general model of the pseudo-Jahn-Teller effect (PJTE). A qualitative application of PJTE would predict all the X3 species to be transition-state structures that relax to the distorted X ---X-X and X-X— X entities. The VBSCD makes a distinction between strong binders, which form transition states, and weak binders that form stable intermediate clusters. Thus, the VBSCD model is in tune with the general observation that as one moves in the periodic table from strong binders to weak ones (e.g., metallic) matter changes from discrete molecules to extended delocalized clusters and/or lattices. The delocalized clusters of the strong binders are the transition states for chemical reactions. 

Another factor contributing to the asymmetry and breadth of absorption bands in crystal field spectra of transition metal ions is the dynamic Jahn-Teller effect, particularly for dissolved hexahydrated ions such as [Fe(H20)6]2+ and [Ti(H20)6]3+, which are not subjected to static distortions of a crystal structure. The degeneracies of the excited 5Eg and 2Eg crystal field states of Fe2+ and Ti3+, respectively, are resolved into two levels during the lifetime of the electronic transition. This is too short to induce static distortion of the ligand environment even when the cations occupy regular octahedral sites as in the periclase structure. A dual electronic transition to the resolved energy levels of the Eg excited states causes asymmetry and contributes to the broadened absorption bands in spectra of most Ti(m) and Fe(II) compounds and minerals (cf. figs 3.1,3.2 and 5.2). 

The site preferences shown by cations in the spinel structure demonstrate that transition metal ions prefer coordination sites that bestow on them greatest electronic stability. In addition, certain cations deform their surrounding in order to attain enhanced stability by the Jahn-Teller effect. These two features suggest that similar factors may operate and cause enrichments of cations in specific sites in silicate structures, leading to cation ordering or intersite (intracrystalline ) partitioning within individual minerals which, in turn, may influence distribution coefficients of cations between coexisting phases. 

Metals that form relatively stable aqua ions in solntion have generally been well characterized. The hydration nnmbers of the transition metals, for example, have commonly been found to be six, consistent with the results of solid-state studies of crystalline hydrates. Exceptions inclnde Ag+, which has a hydration number of four, and Cn +, which has been found to have four short M-0 interactions and two longer ones, consistent with a Jahn-Teller distortion (see Jahn - Teller Effect) of the complex. The hydration numbers of the lanthanide ions in solution have been the subject of many investigations and some controversy recent resnlts snggest a decrease from nine to eight across the series from Ta + to... 

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