Methyl cation, bonds

An alkyl radical is neutral and has one more electron than the corresponding carbocation Thus bonding m methyl radical may be approximated by simply adding an electron to the vacant 2p orbital of sp hybridized carbon m methyl cation (Figure 4 19a) Alternatively we could assume that carbon is sp hybridized and place the unpaired elec tron m an sp orbital (Figure 4 9b)... 

Substituent effects on intermediates can also be analyzed by MO methods. Take, for example, methyl cations where adjacent substituents with lone pairs of electrons can form 71 bonds, as can be expressed in either valence bond or MO terminology. 

The formation of a further single bond between sulfur and carbon, as in the trimethylsulfonium cation, may be pictured as involving a 3sp3 unshared pair orbital on sulfur and an empty 2sp3 orbital on carbon in a methyl cation. Thus the three a bonds and the remaining unshared pair (in a 3sp3 orbital) in a trialkylsulfonium ion are distributed approximately tetrahedrally, i.e. the ion is pyramidal, with the sulfur atom at the apex (2). 

These ions represent strong nucleophiles which form a covalent bond during recombination with the methyl cation. The resulting CH3—X should be relatively less reactive when attacked by a nucleophile. 

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

Comer protonation leads to a species that could be described as a methyl cation (a known ion) coordinated with a carbon-carbon double bond. 

Alkyl groups are able to decrease the concentration of positive charge on the carbocation by donating electrons inductively, thus increasing the stability of the carbocation. The greater the number of alkyl groups bonded to the positively charged carbon, the more stable is the carbocation. Therefore, a 3° carbocation is more stable than a 2° carbocation, and a 2° carbocation is more stable than a 1° carbocation, which in turn is more stable than a methyl cation. 

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. 

Other mechanisms with the involvement of an incipient methyl cation were also proposed.418,460,462 An attack of methyl cation released from extensively polarized methoxy groups on the carbon-hydrogen bond forms pentacoordinated carbocation intermediates that, in turn, yields ethyl methyl ether after the loss of a proton ... 

However, the methyl cation (in itself a very energetic, unprobable species in the condensed state) is not expected to attack a carbon-hydrogen bond in dimethyl ether (or methanol) in preference to the oxygen atom. The more probable attack on oxygen would lead to the trimethyloxonium ion, which was observed experimentally447,463 On the action of a basic site the trimethyloxonium ion can then be deprotonated to form dimethyloxonium methylide ... 

Methane, with its relatively nonpolar bonds, is inert to almost all reagents that could remove hydrogen as H or H e except under anything but extreme conditions. As would be expected, methyl cations CH3 and methyl anions CH3 e are very difficult to generate and are extremely reactive. For this reason, the following reactions are not observed ... 

Thus, by definition, electrophiles are electron-pair acceptors and nucleophiles are electron-pair donors. These definitions correspond closely to definitions used in the generalized theory of acids and bases proposed by G. N. Lewis (1923). According to Lewis, an acid is any substance that can accept an electron pair, and a base is any substance that can donate an electron pair to form a covalent bond. Therefore acids must be electrophiles and bases must be nucleophiles. For example, the methyl cation may be regarded as a Lewis acid, or an electrophile, because it accepts electrons from reagents such as chloride ion or methanol. In turn, because chloride ion and methanol donate electrons to the methyl cation they are classified as Lewis bases, or nucleophiles ... 

Ionic or polar reactions of alkyl halides rarely are observed in the vapor phase because the energy required to dissociate a carbon-halogen bond heterolyti-cally is almost prohibitively high. For example, while the heat of dissociation of chloromethane to a methyl radical and a chlorine atom is 84 kcal mole-1 (Table 4-6), dissociation to a methyl cation and a chloride ion requires about 227 kcal mole-1 ... 

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