Planar carbon transition states

It has also been previously shown73 that the fluctuation pattern of electron density in the ELF basins provides a consistent description of pseudopericyclic and pericyclic bonding in concerted processes such as thermal chelotropic decarbonilation reactions.74 Experimental support for planar pseudopericyclic transition states in chelotropic decar-bonilations has been recently reported.75 ELF picture of bonding reveals that for the eight transition states analysed (see Scheme 3), the departing CO can be visualized in terms of a carbon monoxide structure with a Tone pair region on the carbon atom. 

To understand why a racemic product results from the reaction of T120 wjtl 1-butene, think about the reaction mechanism. 1-Butene is first protonaled tc yield an intermediate secondary (2°) carbocation. Since the trivalent carbon i sp2-hybridized and planar, the cation has no chirality centers, has a plane o symmetry, and is achiral. As a result, it can react with H20 equally well fron either the top or the bottom. Reaction from the top leads to (S)-2-butano through transition state 1 (TS 1) in Figure 9.15, and reaction from the bottorr leads to R product through TS 2. The two transition states are mirror images. The] therefore have identical energies, form at identical rates, and are equally likeb to occur. 

Figure 11.4 The transition state of an Sjvj2 reaction has a planar arrangement of the carbon atom and the remaining three groups. Electrostatic poten tial maps show that negative charge (red) is delocalized in the transition state.

All are tertiary halides so that attack by the S mode would not be expected to occur on (16) or (17) any more than it did on (8) (cf. p. 82). Sn2 attack from the back on the carbon atom carrying Br would in any case be prevented in (16) and (17) both sterically by their cagelike structure, and also by the impossibility of forcing their fairly rigid framework through transition states with the required planar distribution of bonds to the bridgehead carbon atom (cf. p. 84). Solvolysis via rate-limiting formation of the ion pair (SN1), as happens with (8) is... 

Why does C4H8 adopt puckered D2d geometry As shown in Fig. 3.82, the skeletal carbon atoms twist out of planarity (with dihedral cccc = 17.9°), allowing each methylenic hydrogen to be distinguished as axial (with cccH(a) = 94.9°) or equatorial (with cccH(e) = 138.7°). The puckered equilibrium structure lies only 0.8 kcal mol-1 below the transition-state D4h structure. 

Scheme 3.2-S. Transformations with conservation of 2e aromaticity. 6a is a derivative of IB (Scheme 3.2-2) and has a planar tetracoordinate carbon atom. The dashed lines of the transition state 7 represent two 3c2e bonds (BBB and CBB).

There are two simple ways in which the SN2 reaction of methyl chloride could occur with hydroxide ion. These differ in the direction of approach of the reagents (Figure 8-1). The hydroxide ion could attack chloromethane at the front side of the carbon where the chlorine is attached or, alternatively, the hydroxide ion could approach the carbon on the side opposite from the chlorine in what is called the back-side approach. In either case, the making of the C-O bond is essentially simultaneous with the breaking of the C-Cl bond. The difference is that for the back-side mechanism the carbon and the attached hydrogens become planar in the transition state. 

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