Double rotation about

Figure B2.4.1. Proton NMR spectra of the -dimethyl groups in 3-dimethylamino-7-methyl-l,2,4-benzotriazine, as a fiinction of temperature. Because of partial double-bond character, there is restricted rotation about the bond between the dunethylammo group and the ring. As the temperature is raised, the rate of rotation around the bond increases and the NMR signals of the two methyl groups broaden and coalesce.

The carbon atoms of the double bond have a trigonal planar configuration and free rotation about the C—C bond is prevented by the n bond. The inability to rotate means that geometrical isomers can be produced, with substituents a and b, thus ... 

In principle cis 2 butene and trans 2 butene may be mterconverted by rotation about the C 2=C 3 double bond However unlike rotation about the C 2—C 3 single bond in butane which is quite fast mterconversion of the stereoisomeric 2 butenes does not occur under normal circumstances It is sometimes said that rotation about a carbon-carbon double bond is restricted but this is an understatement Conventional lab oratory sources of heat do not provide enough energy for rotation about the double bond m alkenes As shown m Figure 5 2 rotation about a double bond requires the p orbitals of C 2 and C 3 to be twisted from their stable parallel alignment—m effect the tt com ponent of the double bond must be broken at the transition state... 

Isomeric alkenes may be either constitutional isomers or stereoisomers There is a sizable barrier to rotation about a carbon-carbon double bond which corresponds to the energy required to break the rr component of the double bond Stereoisomeric alkenes are configurationally stable under normal conditions The configurations of stereoisomeric alkenes are described according to two notational systems One system adds the prefix CIS to the name of the alkene when similar substituents are on the same side of the double bond and the prefix trans when they are on opposite sides The other ranks substituents according to a system of rules based on atomic number The prefix Z is used for alkenes that have higher ranked substituents on the same side of the double bond the prefix E is used when higher ranked substituents are on opposite sides... 

Geometrical Isomerism. Rotation about a carbon-carbon double bond is restricted because of interaction between the p orbitals which make up the pi bond. Isomerism due to such restricted rotation about a bond is known as geometric isomerism. Parallel overlap of the p orbitals of each carbon atom of the double bond forms the molecular orbital of the pi bond. The relatively large barrier to rotation about the pi bond is estimated to be nearly 63 kcal mol (263 kJ mol-i). 

Freedom of rotation about the double methylene bridge in the compound (7) (dimethyl 4,4 -(l,2-ethanediyl)bisben2oate [797-21-7]) destroys the rod shape of the molecule and prevents Hquid crystal formation. The stilbene derivative (8) (dimethyl 4,4 -(l,2-ethenediyl)bisben2oate [10374-80-8]) however, is essentially linear and more favorable for Hquid crystal formation. 

In Eq. (2), the dihedral tenn includes parameters for the force constant, Ky, the periodicity or multiplicity, n and the phase, 8. The magnimde of Ky dictates the height of the barrier to rotation, such that Ky associated with a double bond would be significantly larger that that for a single bond. The periodicity, n, indicates the number of cycles per 360° rotation about the dihedral. In the case of an bond, as in ethane, n would... 

The activation energy for rotation about a typical carbon-carbon double bond is very high—on the order of 250 kj/mol (about 60 kcal/ mol). This quantity may be taken as a measure of the tt bond contribution to the total C=C bond strength of 605 kJ/mol (144.5 kcal/mol) in ethylene and compares closely with the value estimated by manipulation of thermochemical data on page 191. 

Rotation about single bonds and conformational changes can be studied. Amides constitute a classic example. Because of the partial double bond character of the carbon-nitrogen bond as a consequence of the contribution of 2 to the electronic structure, there is an energy barrier to rotation about this bond. 

The 180° trans structure is only about 2.5 kcal/mol higher in energy than the 0° conformation, a barrier which is quite a bit less than one would expect for rotation about the double bond. We note that this structure is a member of the point group. Its normal modes of vibration, therefore, will be of two types the symmetrical A and the non-symmetrical A" (point-group symmetry is maintained in the course of symmetrical vibrations). 

Some derivatives of triafulvene undergo rotation about the carbon-carbon double bond even at room temperature. Given that cis-trans isomerization about double bonds is normally very difficult (see Chapter 7, Problem 1), how would you rationalize this Examine the electrostatic potential map for perpendicular hexaphenyltriafulvene (the rotational transition state).Would polar solvents tend to lower or raise the rotation barrier Explain. 

The cation of 4,4 -biquinazolinyl and its 2,2 -dimethyl derivative readily add water across the 3,4- and 3, 4 -double bonds, but the cation of 2,2 -biquinazolinyl is not hydrated. Hydration in the 4,4 -isomers has been attributed to restricted rotation about the 4,4 -bond, a steric effect which is relieved by hydration. The ultraviolet spectrum of 2,2 -biquinazolinyl (neutral species and cation) shows that there is considerable conjugation between the quinazoline groups. Covalent hydration is absent from the latter compound because it would otherwise destroy the extended conjugation present. 

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. 

In the cis isomer, the two CH3 groups (or the two H atoms) are as close to one another as possible. In the trans isomer, the two identical groups are farther apart. The two forms exist because there is no free rotation about the carbon-to-carbon double bond. The situation is analogous to that with cis-trans isomers of square planar complexes (Chapter 15). In both cases, the difference in geometry is responsible for isomerism the atoms are bonded to each other in the same way. 

For 6, the activation energy for rotation about the MSi bond has been measured as AG = 40.3 (+ 5) kJ/mol [143]. According to MO calculations, a genuine Cr = Si double bond has no rotational barrier worth mentioning. This applies also, with some restrictions, to the discussed base adducts. 

They found no evidence of (Z)/(E)-isomerism in the diazosulfones formed. This may be due to the lowering of the barrier of rotation about the NN double bond by the contributions of expanded octet structures such as 6.17 b. It is therefore likely that the observed diazosulfones are ( -compounds. 

The presence of a carbon-carbon double bond strongly influences the shape of a molecule because it prevents one part of a molecule from rotating relative to another part. The double bond of ethene, for example, holds the entire molecule flat. Figure 3.19 shows that the two 2p-orbitals overlap best if the two CH2 groups lie in the same plane. In order for the molecule to rotate about the double bond, the u-bond would need to break and reform. 

Double bonds and their influence on molecular shape are vitally important for living organisms. For instance, they enable you to read these words. Vision depends on the shape of the molecule retinal in the retina of the eye. cis-Retinal is held rigid by its double bonds (41). When light enters the eye, it excites an electron out of the iT-bond marked by the arrow. The double bond is now weaker, and the molecule is free to rotate about the remaining o-bond. When the excited electron falls back, the molecule has rotated about the double... 

S A discussion of rotation about a double bond on the basis of the quantum mechanics has been published by E. Hiickel, Z. Physik, 60, 423 (1930), which is, I feel, neither so straightforward nor so convincing as the above treatment, inasmuch as neither the phenomenon of concentration of the bond eigenfunctions nor that of change in quantization is taken into account. 

---