Inner sphere rearrangement

Inner Sphere Rearrangement With Flow of Charge ... 

Coordination compounds are known for their photochemical properties, which may result in photodissociation, photosubstitution, photoisomerization, photoreduction, or photooxidation, for example (3). In addition to inner-sphere rearrangements, the complexes in excited states are susceptible to transfer their energy or charges into other species, such as solvent molecules, ion-pair partners, and other nonbonded quenchers. 

A part of the activation energy will arise from the adjustment to a common value in both complexes (inner-sphere rearrangement energy). 

Ru(OHj)g also implies a much smaller value for Fe(OH2) because the inner-sphere rearrangement is greater for Fe than for Ru (see Table 6.1). In a similar vein, it should be noted that the difference in ionic radii of V(II) and V(III) is very similar to that of Fe(II) and Fe(III), so that the Fe(OH2)6 exchange rate might be expected to be -0.01 M s . On the... 

Diels-alder adducts at 0°C. This cation radical-vinylcyclobutane rearrangement is non-stereospecific, thus accounting for the formation of a cis-trans mixture of Diels-Alder adducts. Kinetic studies revealed (Scheme 8) that the ionization of these ethers involves an inner-sphere electron-transfer mechanism involving strong covalent (electrophilic) attachment to the substrate via oxygen (oxonium ion) or carbon (carbocation). 

This article is concerned with reactions in which the net effect is transfer of one or more electrons, with little permanent rearrangement of the structures surrounding the donor and acceptor sites. Typical examples are the following an outer-sphere reaction (equation 1), an inner-sphere reaction (equation 2) that involves direct bridging Cr-Cl-Cr in the transition state, and a two-electron reaction (equation 3) that could be classed as atom transfer, but is formally analogous to equation (2). 

The reduction of 69 by iodide ion proceeds by an inner-sphere process involving prereductive association (173). The electrochemical reduction involves a single, chemically reversible two-electron transfer at 0.0 V (174). The large peak separations observed in the cyclic voltammograms of 69, at Hg, Pt, or Au electrodes, are due to slow charge-transfer kinetics for the reduction process the slowness of the electron transfer may arise from the accompanying structural rearrangement (174). 

When reactions involve bonds rearrangement, or adsorption, the reacting species looses a part of its solvation shell and moves close to the electrode surface. They are called inner sphere electron transfer reactions and the electronic interactions with the electrode can be either weak or strong. Depending on the elec-... 

A general conclusion is that the e -donors gain a tremendous reactivity advantage by the opening of inner-sphere pathways, because bond rearrangements within a bridged transition state are complementary within the restriction on nuclear motion... 

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