Parameters electron delocalization

There is also substantial stabilization of [4+] by electron delocalization from the cyclic a-vinyl group. This is shown by a comparison of the thermodynamic driving force (p Tr lies between —7.8 and —8.5) and absolute rate constant (ks = 1 -6 x 107 s 1) for the reaction of [4+] in 25% acetonitrile in water with the corresponding parameters for reaction of the resonance-stabilized l-(4-methoxyphenyl)ethyl carbocation in water (p Tr = — 9.4and s= 1 x 108 s Table 5). 

The observed difference in the parameters is due most likely to the electron delocalization in the aromatic ring and, hence, to the increase in the triplet repulsion. The difference between the Eeo values for the reactions considered amounts to 13kJmol-1. With allowance for the examples considered above, Equation (6.39) can be extended and written in the following form ... 

The next cyclic alkadiene, 1,3-cyclopentadiene, has been experimentally studied by MW, GED and XR methods. The carbon skeleton is planar (C2v symmetry), and the small C=C—C angles compared to those in 1,3-butadiene (124.3°) or d.s-1-butene (126.40)58 do not seem to influence noticeably the lengths of the CC bonds, although other effects, such as 7r-electron delocalization, might have an opposite effect. The apparently normal structure parameters observed for 1,3-cyclopentadiene might therefore be a result of different forces having opposite effects on the structure parameters. 

The results for Cr34 and the 3d5 cations Fe3+ and Mn2+ show that it is possible to derive values of the Racah B parameter for transition metal compounds from absorption bands in their crystal field spectra, enabling comparisons to be made with field-free ion values. In all cases, there is a decrease of the Racah B parameter for the bonded cations relative to the gaseous ions, which is indicative of diminished repulsion between 3d electrons in chemical compounds of the transition metals. This reduction is attributable to electron delocalization or covalent bonding in the compounds. Such decreases of Racah B parameters are expressed as the nephelauxetic Greek , cloud expanding) ratio, p, given by... 

The delocalizability parameter is based on a perturbational MO treatment of a partial electron delocalization between two molecules when they approach each other (Fukui, 1970). More precisely, it characterizes the site-specific energy stabilization due to a fractional electron transfer to or from a reagent. Dependent on the donor or acceptor capability of the molecule of interest, the occupied or unoccupied MO energies and wavefunction contributions at the reaction site are considered. 

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