Overlap of p orbitals

The TT bond in ethylene generated by overlap of p orbitals of adjacent carbons... 

Although both stereoisomers yield 4 tert butylcyclohexene as the only alkene they do so at quite different rates The cis isomer reacts over 500 times faster than the trans The difference in reaction rate results from different degrees of rr bond develop ment in the E2 transition state Since rr overlap of p orbitals requires their axes to be parallel rr bond formation is best achieved when the four atoms of the H—C—C—X unit he in the same plane at the transition state The two conformations that permit this are termed syn coplanar and anti coplanar... 

Bonding m alkenes is described according to an sp orbital hybridization model The double bond unites two sp hybridized carbon atoms and is made of a ct component and a rr component The ct bond arises by over lap of an sp hybrid orbital on each carbon The rr bond is weaker than the CT bond and results from a side by side overlap of p orbitals... 

TT bond (Section 2 20) In alkenes a bond formed by overlap of p orbitals in a side by side manner A tt bond is weaker than a u bond The carbon-carbon double bond in alkenes con sists of two sp hybridized carbons joined by a a bond and a TT bond... 

A carbon-carbon double bond is stronger than one carbon-carbon single bond but weaker than the sum of two single bonds (Section 2.15). A carbon-carbon triple bond is weaker than the sum of three carbon-carbon single bonds. Recall that a single C—C bond is a o-bond, but the additional bonds in a multiple bond are TT-bonds. One reason for the difference in strength is that the side-by-side overlap of p-orbitals that results in a rr-bond is not as great as the end-to-end overlap that results in a o-bond. 

Because carbon stands at the head of its group, we expect it to differ from the other members of the group. In fact, the differences between the element at the head of the group and the other elements are more pronounced in Group 14/IV than anywhere else in the periodic table. Some of the differences between carbon and silicon stem from the smaller atomic radius of carbon, which explains the wide occurrence of C=C and G=Q double bonds relative to the rarity of Si=Si and Si=0 double bonds. Silicon atoms are too large for the side-by-side overlap of p-orbitals necessary for -it-bonds to form between them. Carbon dioxide, which consists of discrete 0=C=0 molecules, is a gas that we exhale. Silicon dioxide (silica), which consists of networks of —O—Si- O - groups, is a mineral that we stand on. 

FIGURE 1.7 Overlap of p orbitals in a triple bond. For clarity, the a orbitals have been... 

In contrast with exo (top) facial selectivity in the additions to norbomene 80 [41], Diels-Alder reaction between isodicyclopentadiene 79 takes place from the bottom [40] (see Scheme 32). To solve this problem, Honk and Brown calculated the transition state of the parent Diels-Alder reaction of butadiene with ethylene [47], They pointed ont that of particular note for isodicyclopentadiene selectivity issue is the 14.9° out-of-plane bending of the hydrogens at C2 and C3 of butadiene. The bending is derived from Cl and C4 pyramidalization and rotation inwardly to achieve overlap of p-orbitals on these carbons with the ethylene termini. To keep the tr-bonding between C1-C2 and C3-C4, the p-orbitals at C2 and C3 rotate inwardly on the side of the diene nearest to ethylene. This is necessarily accompanied by C2 and C3 hydrogen movanent toward the attacking dienophile. They proposed that when norbomene is fused at C2 and C3, the tendency of endo bending of the norbomene framework will be manifested in the preference for bottom attack in Diels-Alder reactions (Schane 38). 

The requirements necessary for the occurrence of aromatic stabilisation, and character, in cyclic polyenes appear to be (a) that the molecule should be flat (to allow of cyclic overlap of p orbitals) and (b) that all the bonding orbitals should be completely filled. This latter condition is fulfilled in cyclic systems with 4n + 2n electrons (HuckeVs rule), and the arrangement that occurs by far the most commonly in aromatic compounds is when n = 1, i.e. that with 6n electrons. IO71 electrons (n = 2) are present in naphthalene [12, stabilisation energy, 255 kJ (61 kcal)mol-1], and I4n electrons (n = 3) in anthracene (13) and phenanthrene (14)—stabilisation energies, 352 and 380 kJ (84 and 91 kcal) mol- respectively ... 

The sideway overlap of p orbitals results in the formation of a it bond. 

Figure 3.11. Overlap of 5 orbitals gives rise to an 5 band, and overlap of p orbitals gives rise to a p band. The 5 and p orbitals of the atoms can be so widely spaced that there is a bandgap. In many cases the separation is less and the bands overlap.

The differences arise from the nature of the Jt orbitals in the double bond system. Consider 1,4-pentadiene first. We may draw this to show overlap of p orbitals to create two separate n bonds, and effectively that is all there is that is worthy of note (Figure 2.24). The double bonds are isolated entities that do not interact. 

With a double bond, rotation would destroy the tt bond that arises from overlap of p orbitals consequently, there is a very large barrier to rotation. It is of the order of 263 kJmol , which is very much higher than any of the barriers to rotation about single bonds that we have seen for conformational isomerism. Accordingly, cis and trans isomers do not interconvert under normal conditions. Ring systems can also lead to geometric isomerism, and cis and trans isomers... 

The rr bond of an alkene results from overlapping of p orbitals and provides regions of increased electron density above and below the plane of the molecule. These electrons are less tightly bound than those in the a bonds, so are more polarizable and can interact with a positively charged electrophilic reagent. This forms the first part of an electrophilic addition, in which the electrons are used to form a a bond with the electrophile and leave the other carbon of the double bond electron deficient, i.e. it becomes a carbocation. This carbocation is then rapidly captured by a nucleophile, which donates its... 

Overlapping of p orbitals strengthens bonds, and bond energies are greatest for triple and smallest for single bonds. 

The formation of alicyclics by electrocyclic and cycloaddition reactions (Section 9.4) proceeds by one-step cyclic transition states having little or no ionic or free-radical character. Such pericyclic (ring closure) reactions are interpreted by the Woodward-Hoffmann rules in the reactions, the new a bonds of the ring are formed from the head-to-head overlap of p orbitals of the unsaturated reactants. 

Generation of a carbocation by ionization permits cyclic overlap of p orbitals on each C. With six w electrons, the cation is aromatic ( = 1). 

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