Solvent redistribution

This is no longer the case when (iii) motion along the reaction patir occurs on a time scale comparable to other relaxation times of the solute or the solvent, i.e. the system is partially non-relaxed. In this situation dynamic effects have to be taken into account explicitly, such as solvent-assisted intramolecular vibrational energy redistribution (IVR) in the solute, solvent-induced electronic surface hopping, dephasing, solute-solvent energy transfer, dynamic caging, rotational relaxation, or solvent dielectric and momentum relaxation. 

Excess alkylating reagent is required if the tetraorganotin is desired as the exclusive product. In commercial practice, the stoichiometry is kept at or below 4 1, since the cmde product is usually redistributed to lower organotin chlorides in a subsequent step and an ether is used as the solvent (86). The use of diethyl ether in the Grignard reaction has been generally replaced with tetrahydrofuran. 

The free energy of activation at the QCISD(T)/6-31 H-- -G(d,p) level amounts to 21.1 kcal/mol. According to the authors, the large electron density redistribution arising upon cyclization makes it necessary to use extended basis sets and high-order electron correlation methods to describe the gas-phase thermodynamics, which indicates clearly the gas-phase preference of the azido species. However, the equilibrium is shifted toward the tetrazole as the polarity of a solvent is increased. For instance, SCRF calculations (e = 78.4) yield a relative free energy of solvation with respect to the cw-azido isomer of —2.4 kcal/mol for the tmns-zziAo compound and of —6.8 kcal/mol for the tetrazole isomer. At a much lower level, the... 

Nonpolarizable interfaces correspond to interfaces on which a reversible reaction takes place. An Ag wire in a solution containing Ag+ions is a classic example of a nonpolarizable interface. As the metal is immersed in solution, the following phenomena occur3 (1) solvent molecules at the metal surface are reoriented and polarized (2) the electron cloud of the metal surface is redistributed (retreats or spills over) (3) Ag+ ions cross the phase boundary (the net direction depends on the solution composition). At equilibrium, an electric potential drop occurs so that the following electrochemical equilibrium is established ... 

Since a metal is immersed in a solution of an inactive electrolyte and no charge transfer across the interface is possible, the only phenomena occurring are the reorientation of solvent molecules at the metal surface and the redistribution of surface metal electrons.6,7 The potential drop thus consists only of dipolar contributions, so that Eq. (5) applies. Therefore the potential of zero charge is directly established at such an interface.3,8-10 Experimentally, difficulties may arise because of impurities and local microreactions,9 but this is irrelevant from the ideal point of view. 

Given their extraordinary reactivity, one might assume that o-QMs offer plentiful applications as electrophiles in synthetic chemistry. However, unlike their more stable /tora-quinone methide (p-QM) cousin, the potential of o-QMs remains largely untapped. The reason resides with the propensity of these species to participate in undesired addition of the closest available nucleophile, which can be solvent or the o-QM itself. Methods for o-QM generation have therefore required a combination of low concentrations and high temperatures to mitigate and reverse undesired pathways and enable the redistribution into thermodynamically preferred and desired products. Hence, the principal uses for o-QMs have been as electrophilic heterodienes either in intramolecular cycloaddition reactions with nucleophilic alkenes under thermodynamic control or in intermolecular reactions under thermodynamic control where a large excess of a reactive nucleophile thwarts unwanted side reactions by its sheer vast presence. 

The solvent reorganization term reflects the changes in solvent polarization during electron transfer. The polarization of the solvent molecule can be divided into two components (1) the electron redistribution of the solvent molecules and (2) the solvent nuclear reorientation. The latter corresponds to a slow and rate-determining step involving the dipole moments of the solvent molecules that... 

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