Rapid exchange

Protonation of formic acid similarly leads, after the formation at low temperature of the parent carboxonium ion, to the formyl cation. The persistent formyl cation was observed by high-pressure NMR only recently (Horvath and Gladysz). An equilibrium with diprotonated carbon monoxide causing rapid exchange can be involved, which also explains the observed high reactivity of carbon monoxide in supera-cidic media. Not only aromatic but also saturated hydrocarbons (such as isoalkanes and adamantanes) can be readily formylated. 

Reactions with Alcohols. The tendency of titanium(IV) to reach coordination number six accounts for the rapid exchange of alkoxy groups with alcohols. Departure of an alkoxy group with the proton is the first step in the ultimate exchange of all four alkoxyls. The four-coordinated monomer is expected to react... 

The efficiency of reduction of benzophenone derivatives is greatly diminished when an ortho alkyl substituent is present because a new photoreaction, intramolecular hydrogen-atom abstraction, then becomes the dominant process. The abstraction takes place from the benzylic position on the adjacent alkyl chain, giving an unstable enol that can revert to the original benzophenone without photoreduction. This process is known as photoenolization Photoenolization can be detected, even though no net transformation of the reactant occurs, by photolysis in deuterated hydroxylic solvents. The proton of the enolic hydroxyl is rapidly exchanged with solvent, so deuterium is introduced at the benzylic position. Deuterium is also introduced if the enol is protonated at the benzylic carbon by solvent ... 

With certain carbonyl compounds, however, such as 3-keto steroids, the isotopic composition is poor due to the rapid exchange of the activated a-hydrogens in the substrate prior to reduction. The corresponding alcohols, in their thermodynamically more stable configuration, are usually found as... 

These equilibria effect a rapid exchange of N atoms between the various species and only a single N nmr signal is seen at the weighted average position of HNO3, [NOa]" " and [N03]. They also account for the high electrical conductivity of the pure (stoichiometric) liquid (Table 11.13), and are an important factor in the chemical reactions of nitric acid and its non-aqueous solutions see below. 

An X-ray crystallographic study of 2-hydroxy-4,6-dimethylpyrimi-dine led to no conclusions regarding its structure. Because of the rapid exchange of the NH protons of pyrimidin-2-one both in dimethyl sulfoxide and in water, nuclear magnetic resonance spectroscopy does not afford positive evidence for either the oxo or the hydroxy formulation. The statement that 4,6-dimethylpyrimidin-2-one had been isolated in two modifications, 94 and 95, was soon disproved. ... 

Rapid exchange of positions was observed for acyl and amidoyl groups in the NMR spectra of compounds 36 in 1-chloronaphthalene solution at high temperatures (170-215°C) (Scheme 18). [72JCS(CC)709]. Crossover experiments clearly indicated the intermolecular exchange. The value of the free-energy barrier was determined as AG = 100 kJ mol at the coales-... 

Dipyrromethenes rapidly exchange the hydrogen atom attached to nitrogen, and the two isomers of unsyramctrical compounds (e.g, 19 and 20) cannot be separately isolated/ Dipyrromethenes form meso-... 

Tne free nitrone is rapidly exchanging with the complexed one. 

We have done our experiments with hectorite, which is a 2 1 smectite that develops negative layer charge by substitution of Li for Mg in the octahedral sheet.Samples were prepared by multiple exchange in 1.0 and 0.1 M CsCl solutions until essentially complete Cs-exchange was reached (97% of the interlayer cations). Temperature dependent data are essential to interpret the results, because there is rapid exchange of Cs among different interlayer sites at room temperature (RT). 

Fig. 5a-c. Theoretical 2H NMR spectra in the rapid exchange limit for the motional mechanisms depicted schematically in Fig. 4 a Kink-3-bond motion b crankshaft-S-bond motion c 180° jump of phenyl ring... 

Note These are examples of important transporters involved in substrate and ADP uptake into the matrix compartment as indicated, and most are reversible. These transporters are proteins and several have been isolated and sequenced. Other specific carriers occur in mitochondria from other tissues. The inner membrane does not allow rapid exchange of NAD or CoA but there are mechanisms for the slow uniport of cofactors synthesized extramitochondrially. 

CpFe(CO)[FcC(NCy)2] results in rapid exchange of CO at 25 °C. Heating this solution to 80 °C results in the partial formation of the carbamoyl species by a formal CO insertion into an Fe-N bond (Scheme 136). ... 

Another major process at the Earth s surface not involving rapid exchange is the chemical weathering of rocks and dissolution of exposed minerals. In some instances the key weathering reactant is H30 in rainwater (often associated with the atmospheric sulfur cycle), while in other cases H30" comes from high concentrations of CO2, e.g., in vegetated soils. 

Large amounts of carbon are found in the terrestrial ecosystems and there is a rapid exchange of carbon between the atmosphere, terrestrial biota, and soils. The complexity of the terrestrial ecosystems makes any description of their role in the carbon cycle a crude simplification and we shall only review some of the most important aspects of organic carbon on land. Inventories of the total biomass of terrestrial ecosystems have been made by several researchers, a survey of these is given by Ajtay etal.(1979). 

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