Electron disproportionation

There are no compounds containing the simple Hg ion. Instead, a metal-to-metal a-bond produces the Hg2 + Cation through the overlap of the 6s orbitals of two Hg ions and occupation of the bonding MO by two electrons. Disproportionation of the mercurous ion into Hg° and Hg as shown in equation (4), has an Equilibrium Constant of 1.14 X 10 based on standard potentials. Hence, the mercurous ion is stable, but depletion of free Hg + by complexation or precipitation will result in disproportionation. 

Recent ESR data suggest that the final step of proton translocation in complex I involves an endoenergetic electronic disproportionation in the ubisemiquinone pair. If tightly coupled and functioning bovine heart submitochondrial particles are snap... 

Many of the reactions involving transition metals are redox reactions (Chapter 9) involving electron transfer. These can be described by half-equations and by ionic equations formed from the combination of two half-equations (with equal numbers of electrons). Disproportionation is a redox reaction involving the simultaneous increase and decrease in oxidation state of the same element. 

The resulting radical is stabilized by electron delocalization and eventually reacts with either another inhibitor radical by combination (dimerization) or disproportionation or with an initiator or other radical. 

The ground state distribution of electrons in the aluminum atom is lT2T2 3T3/). The oxidation state of aluminum is +3, except at high temperatures where monovalent species such as AIQ, AIF, and AI2 have been spectrally identified At lower temperatures, these compounds disproportionate... 

The NMR spectrum indicates a planar aromatic structure. It has been demonstrated that the dianion is more stable than the radical anion formed by one-electron reduction, since the radical anion disproportionates to cyclooctatetraene and the dianion ... 

A few free radicals are indefinitely stable. Entries 1, 4, and 6 in Scheme 12.1 are examples. These molecules are just as stable under ordinary conditions of temperature and atmosphere as typical closed-shell molecules. Entry 2 is somewhat less stable to oxygen, although it can exist indefinitely in the absence of oxygen. The structures shown in entries 1, 2, and 4 all permit extensive delocalization of the unpaired electron into aromatic rings. These highly delocalized radicals show no tendency toward dimerization or disproportionation. Radicals that have long lifetimes and are resistant to dimerization or other routes for bimolecular self-annihilation are called stable free radicals. The term inert free radical has been suggested for species such as entry 4, which is unreactive under ordinary conditions and is thermally stable even at 300°C. ... 

Nitric oxide is the simplest thermally stable odd-electron molecule known and, accordingly, its electronic structure and reaction chemistry have been very extensively studied. The compound is an intermediate in the production of nitric acid and is prepared industrially by the catalytic oxidation of ammonia (p. 466). On the laboratory scale it can be synthesized from aqueous solution by the mild reduction of acidified nitrites with iodide or ferrocyanide or by the disproportionation of nitrous acid in the presence of dilute sulfuric acid ... 

Toluene (methylbenzene) is similar to benzene as a mononuclear aromatic, but it is more active due to presence of tbe electron-donating metbyl group. However, toluene is much less useful than benzene because it produces more polysubstituted products. Most of tbe toluene extracted for cbemical use is converted to benzene via dealkylation or disproportionation. Tbe rest is used to produce a limited number of petro-cbemicals. Tbe main reactions related to tbe cbemical use of toluene (other than conversion to benzene) are the oxidation of the methyl substituent and the hydrogenation of the phenyl group. Electrophilic substitution is limited to the nitration of toluene for producing mono-nitrotoluene and dinitrotoluenes. These compounds are important synthetic intermediates. 

The transition state for disproportionation requires overlap of the p C—H bond undergoing scission and the p-orbital containing the unpaired electron.18 This requirement rationalizes the specificity observed in disproportionation of radicals 29 (Section 1.4,2) and provides an explanation for the persistency of the triisopropylmcthyl radical (33) and related species (Section 1.4.3.2).166 In the case of 33, the P-bydrogens are constrained to lie in the nodal plane of the p-orbital due to stcric buttressing between the methyls of the adjacent isopropyls. 

Disiloxane, tetramesityl-, 3,206 Disproportionation iridium catalysts, 4,1159 Dissolution nuclear fuels, 6, 927 Distannene, 3,217 Distannoxane, 1,3-dichloro-, 3,207 Distibine, tetraphenyl-, 2,1008 Distibines, 2,1008 Disulfido ligands metal complexes, 2,531-540, 553 bonding, 2, 539 electron transfer, 2, 537 intramolecular redox reactions, 2,537 reactions, 2, 537... 

Thus, in the latter case, the term ECE has to be abandoned and replaced by disp . (the SET occurs obviously via a disproportionation process). Finally, the strong base R formed after an overall two-electron reaction is protonated by the solvent or by any acidic impurity. Alternative mechanisms could be proposed taking into account that R or Ar may abstract hydrogen atoms from the solvent ... 

Nitrogen dioxide, N02 (oxidation number -t-4), is a choking, poisonous, brown gas that contributes to the color and odor of smog. The molecule has an odd number of electrons, and in the gas phase it exists in equilibrium with its colorless dimer N204. Only the dimer exists in the solid, and so the brown gas condenses to a colorless solid. When it dissolves in water, NOz disproportionates into nitric acid (oxidation number +5) and nitrogen oxide (oxidation number +2) ... 

An additional important factor affecting the bonding of the heavier group 13 elements is the limited number of valence electrons available for bond formation. In neutral molecules the use of the three valence electrons to form three electron pair bonds necessarily leaves a valence orbital unoccupied. This usually results in association or, in cases where one of the bonds involves another group 13 metal, a disproportionation reaction such as that shown in Eq. (1). 

High yields and stable products result when R = i-Bu and R = Me2N, i-BuO or i-Bu or if R and R are (Me3Si)2CH If substituents with lower electron-releasing capacity are used, the method fails because of disproportionation into AIR 3 + Al. Addition of y-picoline (y-pic) to Al2(i-Bu)4 gives " Al2(i-Bu)4(y-pic)2 with enhanced stability of the metal-metal bond. The action of B2H(j on Al2(i-Bu)4 produces Al2(BH2)4 in which both Al—Al and Al — B bonds occur ". ... 

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