Charge-solvated bridge

Kapota, C. Lemaire, J. Maitre, P. Ohanessian, G. Vibrational signature of charge solvation vs salt bridge isomers of sodiated amino acids in the gas phase. J. Am. Chem. Soc. 2004,126, 1836-1842. 

Scheme 1 Low-energy structures for the complex of and Trp. Structures can be classified as salt-bridge (SB interaction between the positive metal ion and the negative carboxylate of the zwitterionic amino acid) or charge solvation (CS interaction of the metal ion with Lewis-basic sites of the canonical amino acid). Nomenclature of the various structures further includes the main binding sites of the amino acid...

Bidentate chelate (NH2/N7). Uncertain site or chelation. Charge-solvated complex. Salt-bridge complex. 

Let us now return to the question of solvolysis and how it relates to the stracture under stable-ion conditions. To relate the structural data to solvolysis conditions, the primary issues that must be considered are the extent of solvent participation in the transition state and the nature of solvation of the cationic intermediate. The extent of solvent participation has been probed by comparison of solvolysis characteristics in trifluoroacetic acid with the solvolysis in acetic acid. The exo endo reactivity ratio in trifluoroacetic acid is 1120 1, compared to 280 1 in acetic acid. Whereas the endo isomer shows solvent sensitivity typical of normal secondary tosylates, the exx> isomer reveals a reduced sensitivity. This indicates that the transition state for solvolysis of the exo isomer possesses a greater degree of charge dispersal, which would be consistent with a bridged structure. This fact, along with the rate enhancement of the exo isomer, indicates that the c participation commences prior to the transition state being attained, so that it can be concluded that bridging is a characteristic of the solvolysis intermediate, as well as of the stable-ion structure. ... 

FIGURE 1.29. Effect of solvation in the case of a saturated and unsaturated bridge separating two identical oxidizable or reducible groups. B — (N eo/4neo)(l — l/es) NA is Avogadro s number, eo is the electron charge, () the permitivity of vacuum, and es the static dielectric constant of the solvent (+) for oxidations, (—) for reductions. 

In the previous four sections, several solvent radical ions that cannot be classified as molecular ions ( a charge on a solvent molecule ) were examined. These delocalized, multimer radical ions are intermediate between the molecular ions and cavity electrons, thereby bridging the two extremes of electron (or hole) localization in a molecular liquid. While solvated electrons appear only in negative-EAg liquids, delocalized solvent anions appear both in positive and negative-EAg liquids. Actually, from the structural standpoint, trapped electrons in low-temperature alkane and ether glasses [2] are closer to the multimer anions because their stabilization requires a degree of polarization in the molecules that is incompatible with the premises of one-electron models. 

The reaction product of ytterbium metal with benzophenone in a 1 1 molar ratio could be determined by an X-ray structure [278]. The benzophenone dianion unsymmetrically bridges the ytterbium atoms in the HMPA solvate [Yb(OCPh2)2(HMPA)2]2. The aryl oxygen forms a Yb-O bond with a typical terminal bond length (Table 18), but also donates to the other ytterbium. A Yb-C a-bond involving the a-C-atom (2.59(5) A) balances the charge at Yb (II). Reaction of the dianionic complex with four equivalents of phenol HOC6H3tBu2-2,6-Me-4 afforded the mononuclear aryloxide complex Yb(OAr)2(HMPA)2 (Sect. 4.2) [72],... 

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