Methyl cation structure

However, contrary to the parent cation, the corresponding isomeric cyclopropyl-methyl cation structures 58 and 59 are no minimum structures (MP2/6-31G(d)) and do not contribute to the averaged chemical shifts. 

For the analogous 1-methyl-substituted cation [C gCFb]"1", recent experimental investigations and quantum chemical ab initio calculations agree that the dynamics of this cation system can be adequately described by considering only one degenerate set of cations, which have the hypercoordinated puckered methylbicyclobutonium ion structure 420 without contributions from a degenerate set of (l -methylcyclopropyl)methyl cation structures 4217,166,167. 

Dehydration of (2-hydroxymethyl-1,3-butadiene)iron complexes or (hydroxymethyltrimethylenemethane)iron complexes with fluorosulfonic acid/liquid sulfur dioxide generates the corresponding (cross-conjugated dienyljiron cations (194) (equation 72). The H and NMR spectral data for these cations favor an " -TMM-methyl cationic structure (282) over an ) " -isoprenyl cationic stmcture (283). These cations react with water or alcohols to afford butadiene products via nucleophilic attack at C-5. As indicated earlier (Section 6.1.1), the cross-conjugated dienyl cations are believed to be intermediates in the substitution of (193) with weak carbon nucleophiles (Scheme 53). In these cases, nucleophihc attack occurs on C-4 to give predominantly TMM products. ... 

Fig. 5.7. Crystal structures of bis(cyclopropyl)hydroxymethyl cation and 1-cyclopropyl-1-phenylhydroxy-methyl cation. Structural diagrams are reproduced from Ref. 34 with permission.

FIGURE 5 8 Methyl migration in 1 2 2 tnmethylpropyl cation Structure (a) is the initial second ary carbocation structure (b) is the transition state for methyl migration and structure (c) is the final tertiary carbocation... 

Poly(dG-dC) poly(dG-dC) and its methylated analogue structures assume left-handed conformation (Z-DNA) in high molar sodium salt (Na", K" ), in low molar divalent cations (Ca", Mg", Ni ), micromolar concentrations of hexaamine cobalt chloride (Co(NH3)6)Cl3 and in millimolar concentrations of polyamines. In order to analyse the binding of berberine to Z-form DNA, Kumar et al. [186] reported that the Z-DNA structure of poly(dG-dC) poly(dG-dC) prepared in either a high salt concentration (4.0 M) or in 40 mM (Co(NH3)6)Cl3 remained invariant in the presence of berberine up to a nucleotide phosphate/alkaloid molar ratio of 0.8 and suggested that berberine neither bormd to Z-form DNA nor converted the Z-DNA to the... 

Figure 6.8 (a) A stylized orbital structure of the methyl cation. The bonds are... 

C-NMR spectroscopic studies on a-substituted tris(ethynyl)methyl cations 49 prepared from alcohols 50 (equation 18) provided evidence for the participation of resonance structures with allenyl cationic character38. The parent tris(ethenyl)methyl cation (49, R = H) cannot be generated under stable carbocation conditions (SbFs/FSOsH) presumably due to the highly reactive unsubstituted termini of the three ethynyl groups and the resulting low kinetic stability. The chemical shift data (Table 1) give evidence that in all cases Ca and CY are deshielded more than Cg (relative to their precursor alcohols). 

The tert-butyl cation structure (7) with Cs symmetry is better suited for hyperconjugation than the C3h form and is thus energetically slightly favored.29 The energy surface for methyl-group rotation is however very flat. 

The 2-butyl cation is the smallest secondary cation that can be stabilized either by C-C or C-H hyperconjugation. Experimental results give evidence for two equilibrating isomers.33 MP2/6-311G(d,p) calculations show that the symmetrically hydrido-bridged structure 11 is marginally more stable than the partially methyl-bridged structure 10.34 35... 

Correlation with Methyl Cation Affinity. Intrinsic barrier data for some of the other systems we have examined are shown in Table II and Figure 4. Note that the barriers vary widely with structure. Some insight into the mechanism of this variation is obtained by noting that the only thermodynamic parameter which correlates well with the purely kinetic intrinsic barriers is the methyl cation affinity (MCA) of the nucleophile... 

Note that the intrinsic barrier increases with methyl cation affinity. Such a correlation between purely kinetic and purely thermodynamic properties is not surprising in view of theoretical studies (21, 22) which have shown there to be significant contributions to the S 2 transition state from resonance structures such as the following ... 

Many mechanistic implications have been discussed, but we will concentrate here only on the most important structures in the context of dihydrogen-cation complexes. Deuterium-labeled methane and methyl cations were employed to examine the scrambling and dissociation mechanisms. The protonated ethane decomposition yields the ethyl cation and dihydrogen. Under the assumption that the extra proton is associated with one carbon only, a kinetic model was devised to explain the experimental findings, such as H/D scrambling. ... 

Before we move on from the hybrid orbitals of carbon, we should take a look at the electronic structure of important reactive species that will figure prominently in our consideration of chemical reactions. First, let us consider carbanions and carbocations. We shall consider the simplest examples, the methyl anion CHs and the methyl cation CH3+, though these are not going to be typical of the carbanions and carbocations we shall be meeting, in that they lack features to enhance their stability and utility. 

Methyl-1,2,4-triazolo[ 1,5-a]pyrimidin-7-on is amphoteric and can be titrated with perchloric acid in glacial acetic acid (61JOC3834). Some derivatives form isolable hydrohalides (75PHA134). Glier et al. (72T5789) formulated a cationic structure at pH 1 from the UV spectrum contrary to that of Hill et al. (61JOC3834). 

Structures of protonated cyclobutanes have been studied in the same fashion (see Figure 9 B). In the corner-protonated cyclobutane, the structure corresponds essentially to a methyl cation interacting with a trimethylene diyl, and is much less favorable than that for cyclopropane. Similarly, for the edge-protonated ion, the proton must come much closer to the carbons to form a bond than for cyclopropane, and as a result, cyclobutane is much less basic. 

Chemical shift variations among N-methyl cations have been related to electron densities and, in the case of fV-methylpyridinium ions, to Hammett substituent constants.126 Upfield shifts of H,126-128 13C,126 and 14N nuclei126 are observed when electron-donating groups increase the electron density at the quaternized site. In instances where shift differences are large, application of these correlations to molecules giving isomeric products will enable conclusive identification of product structures to be made. 

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