Carbonation potential mapping

The structure of ethylene and the orbital hybridization model for its double bond were presented m Section 2 20 and are briefly reviewed m Figure 5 1 Ethylene is planar each carbon is sp hybridized and the double bond is considered to have a a component and a TT component The ct component arises from overlap of sp hybrid orbitals along a line connecting the two carbons the tt component via a side by side overlap of two p orbitals Regions of high electron density attributed to the tt electrons appear above and below the plane of the molecule and are clearly evident m the electrostatic potential map Most of the reactions of ethylene and other alkenes involve these electrons... 

FIGURE 5 1 (a) The planar framework of u bonds in ethylene showing bond distances and angles (b) and (c) The p orbitals of two sp hybridized carbons overlap to produce a tt bond (d) The electrostatic potential map shows a region of high negative potential due to the tt elec trons above and below the plane of the atoms... 

An sp hybridization model for the carbon-carbon triple bond was developed in Section 2 21 and is reviewed for acetylene in Figure 9 2 Figure 9 3 compares the electrostatic potential maps of ethylene and acetylene and shows how the second tr bond m acetylene causes a band of high electron density to encircle the molecule... 

FIGURE 9 3 Electro static potential maps of eth yiene and acetylene The region of highest negative charge (red) is associated with the TT bonds and lies between the two carbons in both This electron rich re gion IS above and below the plane of the molecule in ethylene Because acetylene has two TT bonds a band of high electron density encir cles the molecule... 

FIGURE 113 (a) The framework of bonds shown in the tube model of benzene are cr bonds (b) Each carbon is sp hybridized and has a 2p orbital perpendicular to the cr framework Overlap of the 2p orbitals generates a tt system encompass mg the entire ring (c) Electrostatic potential map of benzene The red area in the center corresponds to the region above and below the plane of the ring where the tt electrons are concentrated... 

FIGURE 12 8 Electrostatic potential map of propanoyl cation [(CH3CH2C=0) ] The region of greatest positive charge is associated with the carbon of the C=0 group... 

FIGURE 14 1 Electro static potential maps of (a) methyl fluoride and (b) methyllithium The electron distribution is reversed in the two compounds Carbon IS electron poor (blue) in methyl fluoride but electron rich (red) in methyllithium... 

FIGURE 14 3 (a) The unshared electron pair occupies an sp hybridized orbital in dichlorocarbene There are no electrons in the unhybridized p orbital (b) An electrostatic potential map of dichlorocarbene shows negative charge is concentrated in the region of the unshared pair and positive charge above and below the carbon... 

Learning By Model ing includes models of formaldehyde (H2C=0) and its protonated form (H2C=0H ) Compare the two with respect to their electrostatic potential maps and the degree of positive charge at carbon... 

Examine the electro r static potential map of butanoic acid on t Learning By Modeling and notice how much more in tense the blue color (positive charge) is on the OH hydro gen than on the hydrogens bonded to carbon... 

An orbital hybridization description of bonding m methylamme is shown m Figure 22 2 Nitrogen and carbon are both sp hybridized and are joined by a ct bond The unshared electron pair on nitrogen occupies an sp hybridized orbital This lone parr IS involved m reactions m which amines act as bases or nucleophiles The graphic that opened this chapter is an electrostatic potential map that clearly shows the concentration of electron density at nitrogen m methylamme... 

As useful as molecular models are, they are limited in that they only show the location of the atoms and the space they occupy. Another important dimension to molecular structure is its electron distribution. We introduced electrostatic potential maps in Section 1.5 as a way of illustrating charge distribution and will continue to use them throughout the text. Figure 1.6(d) shows the electrostatic potential map of methane. Its overall shape is similar to the volume occupied by the space-filling model. The most electron-rich regions are closer to carbon and the most electron-poor ones are closer to the hydrogens. 

Problem 1.8 concerned the charge distribution in methane (CH4), chloromethane (CH3CI), and methyllithium (CH3Li). Inspect molecular models of each of these compounds, and compare them with respect to how charge is distributed among the various atoms (carbon, hydrogen, chlorine, and lithium). Compare their electrostatic potential maps. 

The electrophilic site of an acyl cation is its acyl carbon. An electrostatic potential map of the acyl cation from propanoyl chloride (Figure 12.8) illustrates nicely the concentration of positive charge at the acyl carbon, as shown by the blue color. The mechanism of the reaction between this cation and benzene is analogous to that of other electrophilic reagents (Figure 12.9). 

Draw Lewis structures for allyl cation. Where is the positive charge Examine atomic charges as well as the electrostatic potential map for localized and delocalized forms of allyl cation. Which carbon (s) carries the charge in each ... 

Compare atomic charges and electrostatic potential maps for imidazole NH protonated and imidazole Nprotonated. In which ion is the positive charge more delocalized Compare carbon-nitrogen bond distances in each ion to those in imidazole as a standard. Are these distances consistent with the bonding patterns shown above for each ion Draw whatever Lewis structures are needed to describe each ion s geometry and charge distribution. 

Examine and eompare eleetrostatie potential maps for the eycloalkanes. Is there any evidenee of earbon-carbon bonds being espeeially eleetron rieh (subject to electrophilic attack), or of CH bonds being espeeially electron poor (subject to deprotonation) ... 

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