Bonds rotation

Some bonds rotate easily, but others do not. When we look at a structure, we must recognize which bonds rotate and which do not. If a bond rotates easily, each molecule can rotate through the different angular arrangements of atoms. If a bond cannot rotate, however, different angular arrangements may be distinct compounds (isomers) with different properties. 

Drawings that differ only by rotations of single bonds usually represent the same compound. For example, the following drawings all represent n-butane  

Rotation of single bonds. Ethane is composed of two methyl groups bonded by overlap of their sp3 hybrid orbitals. These methyl groups may rotate with respect to each other. 

Rotation about single bonds is allowed, but double bonds are rigid and cannot be twisted. 

Because double bonds are rigid, we can separate and isolate compounds that differ only in how their substituents are arranged on a double bond. For example, the double bond in but-2-ene (CH3—CH=CH—CH3) prevents the two ends of the molecule from rotating. Two different compounds are possible, and they have different physical properties  

In ethane (CH3—CH3), both carbon atoms are sp hybridized and tetrahedral. Ethane looks like two methane molecules that have each had a hydrogen plucked off (to form a methyl group) and are joined by overlap of their sp orbitals 

Not all bonds allow free rotation ethylene, for example is quite rigid. In ethylene, the double bond between the two CH2 groups consists of a sigma bond and a pi bond. When we twist one of the two CH2 groups, the sigma bond is unaffected but the pi bond loses its overlap. The two p orbitals cannot overlap when the two ends of the molecule are at right angles, and the pi bond is effectively broken. 

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Fig. 8.6 A bond rotation in the middle of a molecule may lead to a large movement at the end.

Rosenbluth algorithm can also be used as the basis for a more efficient way to perform ite Carlo sampling for fully flexible chain molecules [Siepmann and Frenkel 1992], ch, as we have seen, is difficult to do as bond rotations often give rise to high energy rlaps with the rest of the system. 

In a systematic search there is a defined endpoint to the procedure, which is reached whe all possible combinations of bond rotations have been considered. In a random search, ther is no natural endpoint one can never be absolutely sure that all of the minimum energ conformations have been found. The usual strategy is to generate conformations until n new structures can be obtained. This usually requires each structure to be generate many times and so the random methods inevitably explore each region of the conformc tional space a large number of times. 

FIGURE 3 4 Potential energy diagram for rotation about the carbon-carbon bond in ethane Two of the hydrogens are shown in red and four in green so as to indicate more clearly the bond rotation... 

For molecules and ions having more than one atom, the extra energy can make the component bonds rotate and vibrate faster (rovibrational energy). Isolated atoms, having no bonds, cannot be excited in this way. 

The necessary molecular rigidity of polybenzamide undoubtedly results from the hindered bond rotation within the planar amide group. 

Thiirane 1,1-dioxides extrude sulfur dioxide readily (70S393) at temperatures usually in the range 50-100 °C, although some, such as c/s-2,3-diphenylthiirane 1,1-dioxide or 2-p-nitrophenylthiirane 1,1-dioxide, lose sulfur dioxide at room temperature. The extrusion is usually stereospeciflc (Scheme 10) and a concerted, non-linear chelotropic expulsion of sulfur dioxide or a singlet diradical mechanism in which loss of sulfur dioxide occurs faster than bond rotation may be involved. The latter mechanism is likely for episulfones with substituents which can stabilize the intermediate diradical. The Ramberg-Backlund reaction (B-77MI50600) in which a-halosulfones are converted to alkenes in the presence of base, involves formation of an episulfone from which sulfur dioxide is removed either thermally or by base (Scheme 11). A similar conversion of a,a -dihalosulfones to alkenes is effected by triphenylphosphine. Thermolysis of a-thiolactone (5) results in loss of carbon monoxide rather than sulfur (Scheme 12). 

Figure 4.3. Energy versus bond rotation in methylsuccinic acid (schematic). The diagram shows the greater stability of staggered as compared with eclipsed forms, and the effect of size and dipole moment of substituents on the barriers. The slope of the curve at any point represents the force opposing rotation there. ( = energy of activation of rotation.) (After Gordon )...

It has been common practice to blend plasticisers with certain polymers since the early days of the plastics industry when Alexander Parkes introduced Parkesine. When they were first used their function was primarily to act as spacers between the polymer molecules. Less energy was therefore required for molecular bond rotation and polymers became capable of flow at temperatures below their decomposition temperature. It was subsequently found that plasticisers could serve two additional purposes, to lower the melt viscosity and to change physical properties of the product such as to increase softness and flexibility and decrease the cold flex temperature (a measure of the temperature below which the polymer compound loses its flexibility). 

In addition to constitution and configuration, there is a third important level of structure, that of conformation. Conformations are discrete molecular arrangements that differ in spatial arrangement as a result of facile rotations about single bonds. Usually, conformers are in thermal equilibrium and cannot be separated. The subject of conformational interconversion will be discussed in detail in Chapter 3. A special case of stereoisomerism arises when rotation about single bonds is sufficiently restricted by steric or other factors that- the different conformations can be separated. The term atropisomer is applied to stereoisomers that result fk m restricted bond rotation. ... 

Sketch a potential energy diagram for rotation around a carbon-carbon bond in propane. Clearly identify each potential energy maximum and minimum with a structural formula that shows the conformation of propane at that point. Does your diagram more closely resemble that of ethane or of butane Would you expect the activation energy for bond rotation in propane to be more than or less than that of ethane Of butane ... 

FIGURE 12.14 Comparison of the deoxy-guanosine conformation in B- and Z-DNA. In B-DNA, the Cl -N-9 glycosyl bond is always in the anti position (lefi). In contrast, in the left-handed Z-DNA structure, this bond rotates (as shown) to adopt the syn conformation. 

Step through the sequence of structures depicting bond rotation in ethane. Plot energy (vertical axis) vs. HCCP torsion angle (horizontal axis). Do the minima correspond to staggered structures Do the maxima correspond tc eclipsed structures If not, to what do they correspond ... 

Ring inversion, leading to interconversion of different ring conformers, is typically as facile a process as single-bond rotation. Particularly important are six-membered rings, where interconversion leads to interchange of axial and equatorial positions. 

The second C-C bond forming step (step C), while occurring after the first irreversible ee determining step (step B), can affect the observed enantioselective outcome of the reaction. If the radical intermediate collapses without rotation (k3 Ict, k5 ke), then the observed ee would be determined by the first C-C bond forming step (ki vs. k2), that is the facial selectivity (Scheme 1.4.6). However, if rotation is allowed followed by collapse, then the rate of both trans pathways (Ic and k ) will proportionally effect the observed ee of the cis epoxide (ks vs. ks). Should bond rotation be permissible, the diastereomeric nature of the radical intermediates 9a and 9b renders the distinct possibility of different observed ee s for frany-epoxides and dy-epoxides. 

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