Sp2 hybridized bonds

Comparison of the elements of the third and fifth groups, both having three unpaired electrons leads to an explanation of their stereochemistry. Boron has one s and two p electrons and thus forms three planar sp2 hybrid bonds, whereas nitrogen possesses three p electrons which form bonds at right angles to each other. The comparison is similar between elements of the sixth group and beryllium, in the former case the unpaired electrons are p electrons thus forming two bonds at 90°, whilst beryllium with one s and one p electron forms two linear sp hybrid bonds. 

There is, however, another type of hybridization possible in the carbon atom in which the zs orbital is hybridized with only two of the 2p orbitals (say the px and py). The three sp2 hybrid bonds will then lie in a plane symmetrically inclined at 1200, leaving the unaltered pz orbital perpendicular to this plane, as shown in fig. 4.08 a. The three hybrid bonds of each carbon atom will then be responsible for the two bonds between it and the hydrogen atoms with which it is associated and also for one bond between it and the other carbon atom. This picture explains the observed interbond angles of 120° but does not... 

Single, double, triple, and aromatic bonds are represented by the symbols —, =,, and However, the bond type may be omitted when suggestive, and sp2-hybridized bonded atoms can be written in lower case letters. So C=C—C=C means 1,3-butadiene, which is equivalent to cccc. Branches are indicated by parentheses, e.g., CC(C)C(=0)0 is isobutyric acid. To specify rings, the atom that closes the ring is numbered and specified, as ClCCCCCl for cyclohexane and clcc2ccccc2ccl for naphthalene. The SMILES notation can be used in chemical structure drawing programs for quick input of a structure by the skilled user. 

For example, in formaldehyde, H2CO, one forms sp hybrids on the C atom on the O atom, either sp hybrids (with one p orbital "reserved" for use in forming the n and 7i orbitals and another p orbital to be used as a non-bonding orbital lying in the plane of the molecule) or sp hybrids (with the remaining p orbital reserved for the n and 7i orbitals) can be used. The H atoms use their 1 s orbitals since hybridization is not feasible for them. The C atom clearly uses its sp2 hybrids to form two CH and one CO a bondingantibonding orbital pairs. 

When two sp2-hybridized carbons approach each other, they form a cr bond by sp2-sp2 head-on overlap. At the same time, the unhybridized p orbitals approach with the correct geometry for sideways overlap, leading to the formation of what is called a pi (ir) bond. The combination of an >p2-sp2 a bond and a 2p-2p 77 bond results iii the sharing of four electrons and the formation of a carbon-carbon double bond (Figure 1.14). Note that the electrons in then-bond occupy the region centered between nuclei, while the electrons in the 77 bond occupy regions on either side of a line drawn between nuclei. 

Like the carbon atoms in ethylene, the carbon atom in formaldehyde is in a double bond and therefore sp2-hybridized. 

Resonance forms differ only in the placement of their tt or nonbonding electrons. Neither the position nor the hybridization of any atom changes from one resonance form to another. In the acetate ion, for example, the carbon atom is sp2-hybridized and the oxygen atoms remain in exactly the same place in both resonance forms. Only the positions of the r electrons in the C=0 bond and the lone-pair electrons on oxygen differ from one form to another. This movement of electrons from one resonance structure to another can be indicated by using curved arrows. A curved arrow always indicates the movement of electrons, not the movement of atoms. An arrow shows that a pair of electrons moves from the atom or bond at the tail of the arrow to the atom or bond at the head of the arrow. 

We saw in Chapter 1 that the carbon-carbon double bond can be described in two ways. In valence bond language (Section 1.8), the carbons are sp2-hybridized and have three equivalent hybrid orbitals that lie in a plane at angles of 120° to one another. The carbons form a cr bond by head-on overlap of sp2 orbitals and a tt bond by sideways overlap of unhybridized p orbitals oriented... 

In the Diels-Alder transition state, the two alkene carbons and carbons 1 and 4 of the diene rehybridize from sp2 to sp 5 to form two new single bonds, while carbons 2 and 3 of the diene remain sp2-hybridized to form the new double bond in the cyclohexene product. We ll study this mechanism at greater length in Chapter 30 but will concentrate for the present on learning more about the characteristics and uses of the Diels-Alder reaction. 

Further evidence for the unusual nature of benzene is that all its carbon-carbon bonds have the same length—139 pm—intermediate between typical single (154 pm) and double (134 pm) bonds. In addition, an electrostatic potential map shows that the electron density in all six carbon-carbon bonds is identical. Thus, benzene is a planar molecule with the shape of a regular hexagon. All C-C—C bond angles are 120°, all six carbon atoms are sp2-hybridized. and each carbon has a p orbital perpendicular to the plane of the six-membered ring. 

Pyrrole (two r s, one /) and imidazole are /ive-membered heterocycles, yet both have six tt electrons and are aromatic. In pyrrole, each of the four. sp2-hybridized carbons contributes one tt electron, and the sp2-hybridized nitrogen atom contributes the two from its lone pair, which occupies a p orbital (Figure 15.9). Imidazole, also shown in Figure 15.9, is an analog of pyrrole that has two nitrogen atoms in a five-membered, unsaturated ring. Both nitrogens are sp2-hybridized, but one is in a double bond and contributes only one electron to the aromatic tt system, while the other is not in a double bond and contributes two from its lone pair. 

The electronic structure of benzyne, shown in Figure 16.19, is that of a highly distorted alkyne. Although a typical alkyne triple bond uses sp-hybridized carbon atoms, the benzyne triple bond uses sp2-hybridized carbons. Furthermore, a typical alkyne triple bond has two mutually perpendicular it bonds formed bv p-p overlap, but the benzyne triple bond has one tt bond formed by p-p overlap and one tt bond formed by sp2 sp2 overlap. The latter tt bond is in the plane of the ring and is very weak. 

Figure 16.19 An orbital picture and electrostatic potential map of benzyne. The benzyne carbons are sp2-hybridized, and the "third" bond results from weak overlap of two adjacent sp2 orbitals.

Carboxylic acids are similar in some respects to both ketones and alcohols. Like ketones, the carboxyl carbon is sp2-hybridized, and carboxylic acid groups are therefore planar with C-C=0 and 0=C-0 bond angles of approximately 120° (Table 20.2). 

A conjugated polyene, as we saw in Section 14.1, is one with alternating double and single bonds. According to molecular orbital (MO) theory, the p orbitals on the sp2-hybridized carbons of a conjugated polyene interact to form a set of... 

To illustrate this rule, consider the ethylene (C2H4) and acetylene (C2H2) molecules. You will recall that the bond angles in these molecules are 120° for ethylene and 180° for acetylene. This implies sp2 hybridization in C2H4 and sp hybridization in C2H2 (see Table 7.4). Using blue lines to represent hybridized electron pairs,... 

You may recall that we discussed the bonding in ethene in Chapter 7. The double bond in ethene and other alkenes consists of a sigma bond and a pi bond. The ethene molecule is planar. There is no rotation about the double bond, since that would require breaking the pi bond. The bond angle in ethene is 120°, corresponding to sp2 hybridization about each carbon atom. The geometries of ethene and the next member of the alkene series, QHg, are shown in Figure 22.6. 

Klasinc and Schulte-Frohlinde (1968), who also used HMO for the investigation of substituted benzene diazonium ions, were the first to realize that the remarkable distortion of bond lengths and angles of the benzene ring by the diazonio group (Sec. 4.2) has a significant influence on its reactivity. They found that the sp2-hybridization at the carbon atoms of the benzene ring varied from 1.75 for C(l) to 2.16 for C(2). 

Unsaturated organic molecules, such as ethylene, can be chemisorbed on transition metal surfaces in two ways, namely in -coordination or di-o coordination. As shown in Fig. 2.24, the n type of bonding of ethylene involves donation of electron density from the doubly occupied n orbital (which is o-symmetric with respect to the normal to the surface) to the metal ds-hybrid orbitals. Electron density is also backdonated from the px and dM metal orbitals into the lowest unoccupied molecular orbital (LUMO) of the ethylene molecule, which is the empty asymmetric 71 orbital. The corresponding overall interaction is relatively weak, thus the sp2 hybridization of the carbon atoms involved in the ethylene double bond is retained. 

FIGURE 3.20 The framework of a-bonds in benzene each carbon atom is sp2 hybridized, and the array of hybrid orbitals matches the bond angles (of 120°) in the hexagonal molecule. The bonds around only one carbon atom are labeled all the others are the same. 

C atom trigonal planar, so 120° bond angle sp2 hybridized. 

Multiple bonds are formed when an atom forms a tr-bond by using an sp or sp2 hybrid orbital and one or more ir-bonds by using unhybridized p-orbitals. The side-by-side overlap that forms a ir-bond makes a molecule resistant to twisting, results in bonds weaker than tr-bonds, and prevents atoms with large radii from forming multiple bonds. 

First, the VB part of the description of benzene. Each C atom is sp2 hybridized, with one electron in each hybrid orbital. Each C atom has a p.-orbital perpendicular to the plane defined by the hybrid orbitals, and it contains one electron. Two sp2 hybrid orbitals on each C atom overlap and form cr-bonds with similar orbitals on the two neighboring C atoms, forming the 120° internal angle of the benzene hexagon. The third, outward-pointing sp2 hybrid orbital on each C atom forms a hydrogen atom. The resulting cr-framework is the same as that illustrated in Fig. 3.20. 

Graphite, the most important component of the lead of pencils, is a black, lustrous, electrically conducting solid that vaporizes at 1700°C. It consists of flat sheets of sp2 hybridized carbon atoms bonded covalently into hexagons like chicken wire (Fig. 5.22). There are also weak bonds between the sheets. In the commercially available forms of graphite, there are many impurity atoms trapped between the sheets these atoms weaken the already weak intersheet bonds and let... 

The carhon-carbon double bond in alkenes is more reactive than carbon-carbon single bonds and gives alkenes their characteristic properties. As we saw in Section 3.4, a double bond consists of a a-bond and a 7r-bond. Each carbon atom in a double bond is sp2 hybridized and uses the three hybrid orbitals to form three cr-bonds. The unhvbridized p-orbitals on each carbon atom overlap each other and form a Tr-bond. As we saw in Section 3.7, the carbon-carbon 7r-bond is relatively weak because the overlap responsible for the formation of the 7r-bond is less extensive than that responsible for the formation of the a-bond and the enhanced electron density does not lie directly between the two nuclei. A consequence of this weakness is the reaction most characteristic of alkenes, the replacement of the 77-bond by two new a-bonds, which is discussed in Section 18.6. 

B Carbon atom of CH, group is sp hybridized and forms four a bonds at 109.5°. The other two carbon atoms are both sp2 hybridized and each forms three bond bond angles are about 120°. 

In diamond, carbon is sp hybridized and forms a tetrahedral, three-dimensional network structure, which is extremely rigid. Graphite carbon is sp2 hybridized and planar. Its application as a lubricant results from the fact that the two-dimensional sheets can slide across one another, thereby reducing friction. In graphite, the unhybridized p-electrons are free to move from one carbon atom to another, which results in its high electrical conductivity. In diamond, all electrons are localized in sp3 hybridized C—C cr-bonds, so diamond is a poor conductor of electricity. 

---