Carbon structural effects

For organic reactions in which positive charge develops on carbon, structural effects on reactivity are enhanced in weakly nucleophilic solvents (14). The effect of alkyl substitution on SN reactions can be quantified by the substituent parameter p, which is much more negative in weakly nucleophilic media [e.g., TFA (14, 20), HFIP (4), or TFE (4)] than in normal alcohol solvents. Apparently in weakly cation solvating media, the electron demand for stabilization of positive charge is met from within the molecule [e.g., by enhanced electron donation from adjacent alkyl groups (4)]. 

The carbonyl carbon of a ketone bears two electron releasing alkyl groups an aldehyde carbonyl group has only one Just as a disubstituted double bond m an alkene is more stable than a monosubstituted double bond a ketone carbonyl is more stable than an aldehyde carbonyl We 11 see later m this chapter that structural effects on the relative stability of carbonyl groups m aldehydes and ketones are an important factor m then rel ative reactivity... 

Any structural effect which reduces the electron deficiency at the tricoordinate carbon will have flie effect of stabilizing the caibocation. Allyl cations are stabilized by delocalization involving the adjacent double bond. 

R.L. McCreery, Carbon Electrodes Structural Effects on Electron Transfer Kinetics, in A.J. Bard, Ed., Electroanalytical Chemistry, Vol 18, Marcel Dekker, New York, 1991. 

Sodium a-sulfonated fatty acid esters of long-chain alcohols have a structural effect on the Krafft point different from that of amphiphiles with short alkyl chains [60]. In a series of homologs with the same total carbon number the Krafft points are highest when the hydrophilic alkyl chain lengths in the a-sulfonated fatty acid and the alcohol are fairly long and equal. In this case the packing of the molecules becomes close and tight. 

Gasteiger HA, Markovic NM, Ross PN Jr. 1996. Structural effects in electrocatalysis Electrooxidation of carbon monoxide on Pt3Sn single-crystal surfaces. Catal Lett 36 1-8. 

Furthermore, we believe that the stabilizing influence of boron in the structure of graphite is connected with enhancement of its acceptor properties, which manifest themselves when Boron atoms substitute carbon atoms in the crystalline structure (hexagon ring) of carbon. Such effects are mentioned in the literature for some types of carbon materials [3] and the influence of boron on TEG can be the similar. 

A critical factor here is the reactivity of the hydrogen by-product that is not only able to gasify the initial surface termination of the carbon fiber but also to etch away the newly formed pyrolytic carbon. This effect is desirable for optimization of the growing structure but additionally slows down the reaction. 

The old and lasting problem of heterogeneous catalysis, the mechanism of alkene hydrogenation, has also been approached from the viewpoint of structure effects on rate. In 1925, Lebedev and co-workers (80) had already noted that the velocity of the hydrogenation of the C=C bond decreases with the number of substituents on both carbon atoms. The same conclusion can be drawn from the narrower series of alkenes studied by Schuster (8J) (series 52 in Table IV). Recently authors have tried to analyze this influence of substituents in a more detailed way, in order to find out whether the change in rate is caused by polar or steric effects and whether the substituents affect mostly the adsorptivity of the unsaturated compounds or the reaetivity of the adsorbed species. Linear relationships have been used for quantitative treatment. 

The conclusions on the mechanism of the double bond hydrogenation on metallic catalysts can be summarized as follows (1) with respect to structure effects on rate, all transition metals behave similarly (2) the reactivity of the unsaturated compounds is governed mostly by the number and size of the substituents on the carbon atoms of the double bond through their influence on adsorptivity (3) the electronic nature of the substituents plays a minor if any role. 

Some information about structure effects on the rate of dehydrogenation of alcohols to aldehydes and ketones on metals is found in the older literature 129-132) from which it follows that secondary alcohols react more easily than the primary alcohols 129) and that the reactivity decreases with the length of the carbon chain 131). Some series can be correlated by the Taft equation using a constants (Ref. 131, series 103, Cu-Cr203 catalyst, 350°C, four points, slope 18 Ref 132, series 104, Cu catalyst, four points, slope 22). Linear relationships have been used in a systematic way by... 

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