Anion relative solvent affinity

Coordination of the anions to the cationic palladium center may strongly depend on the polarity of the reaction medium. Solvation of the ion-pair by protic solvent molecules, such as methanol, is expected to facilitate cation-anion dissociation and therefore render the metal center more electrophilic and more easily accessible for substrate molecules. In relatively apolar solvents, close-contact ion-pairs are generally expected to exist. Anion displacement by substrate molecules may then require the use of noncoordinating anions, such as certain tetraaryl borates [19], with a relatively strong affinity for interaction with the solvent molecules. This will lead to a reduced barrier for displacement of these anions by monomer molecules. 

CT) complex with absorption maxima at 470 and 550nm, was produced. These species were formed only in polar solvents with relatively high proton affinity. The data suggested an intermolecular proton transfer, from electronically excited TNB to the solvent forming the anion... 

Class (3) reactions include proton-transfer reactions of solvent holes in cyclohexane and methylcyclohexane [71,74,75]. The corresponding rate constants are 10-30% of the fastest class (1) reactions. Class (4) reactions include proton-transfer reactions in trans-decalin and cis-trans decalin mixtures [77]. Proton transfer from the decalin hole to aliphatic alcohol results in the formation of a C-centered decalyl radical. The proton affinity of this radical is comparable to that of a single alcohol molecule. However, it is less than the proton affinity of an alcohol dimer. Consequently, a complex of the radical cation and alcohol monomer is relatively stable toward proton transfer when such a complex encounters a second alcohol molecule, the radical cation rapidly deprotonates. Metastable complexes with natural lifetimes between 24 nsec (2-propanol) and 90 nsec (tert-butanol) were observed in liquid cis- and tra 5-decalins at 25°C [77]. The rate of the complexation is one-half of that for class (1) reactions the overall decay rate is limited by slow proton transfer in the 1 1 complex. The rate constant of unimolecular decay is (5-10) x 10 sec for primary alcohols, bimolecular decay via proton transfer to the alcohol dimer prevails. Only for secondary and ternary alcohols is the equilibrium reached sufficiently slowly that it can be observed at 25 °C on a time scale of > 10 nsec. There is a striking similarity between the formation of alcohol complexes with the solvent holes (in decalins) and solvent anions (in sc CO2). 

Substituting in equation 11 the known experimental parameters for phenol dissociation (AG, = 13.8 kcalmol" calculated from the ground-state equilibrium constant, pX, = 10.0), AGt((PhO ) — (PhOH)) of the phenolate/phenol system is about —76 kcalmoH, which is about 10% less than the accepted value for the electrostatic solvation energy of the chloride anion in water, AGe(Cr) = —85 kcalmol". These simple considerations imply that the AGt((PhO ) — (PhOH)) contribution to the overall free energy of solvation is largely electrostatic, and that relatively small differences in the gas-phase proton affinity of the base and in specific solvent-solute interactions of the photoacid and the base determine the relatively narrow (in free-energy units) acidity scale in aqueous solution. It... 

This fundamental parameter quantifies the relative affinity of an ion in the two phases, but it is not directly accessible experimentally because it is associated with a single ionic component. Therefore, to make AGf 1 0 or logP1,0 amenable to direct measurement, an extrathermodynamic assumption must be introduced such as the Grunwald or TATB assumption [139], which states that the cation and the anion of tetraphenylarso-nium tetraphenylborate (TPAs+TPB or TATB) have equal standard Gibbs energies for any pair of solvents [140,141] ... 

It is worth mentioning that two electrons can be simultaneously attached to Au to form the dianion Au shown in Fig. 3. This dianion is stable relative to Au with a total energy difference of 65.6 kcal/mol (65.8 kcal/ mol after ZPVE) although it still remains unstable with respect to the corresponding anion Aus by 28.8 kcal/mol (28.6 kcal/mol after ZPVE). It is responsible for the second adiabatic electron affinity (see Ref. [68]). This first implies that such a dianion may exist in solvent or condensed phase (see Ref. [69] for current review) and second, that it does not exist in the gas phase and, therefore, there is no contradiction with the statement that the smallest stable dianion is Aui2 [70]. 

A number of other metal-based redox-active centers have been incorporated into supramolecular receptors, representative examples of which are displayed in Fig. 5 (Compounds 24-28). Many of these receptors electro-chemically respond to cations. but species that respond to anions and neutral molecules are also known. A number of the cation binders are organometallic crown ether and metallocrown or metallothiacrown derivatives, for example. Compound 24. Flow-ever, in many cases, the redox processes are not particularly reversible, and relatively small anodic shifts in the metal-centered redox couples are observed. A series of self-assembled [12]metallocrown-3 complexes, two of which are 25 and 26, were found by Severin to bind halide salts of small Group 1 metals strongly in organic solvents, with affinities similar to those of the cryptands. X-ray crystal structures revealed that the metal cation was... 

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