Nonplanar

C3.6.13 where large diffusion fluxes are indicated by —> and smaller diffusion fluxes by —+. For tire part of tire B front tliat protmdes into tire A region, fast diffusion of B leads to dispersal of B and suppresses tire autocatalytic reaction tliat requires two molecules of B. The front will have difficulty advancing here. In tire region where A protmdes into B, A will react leading to advancement of tire front. The net effect is to remove any initial nonplanarity and give rise to a planar front. 

FIGURE 3 11 Nonplanar ( puckered ) conformation of cydobutane The nonplanar con formation avoids the eclipsing of bonds on adjacent carbons that characterizes the planar con formation... 

Cyclobutane has less angle strain than cyclopropane and can reduce the torsional strain that goes with a planar geometry by adopting the nonplanar puckered confer matron shown m Figure 3 11... 

A second but much less stable nonplanar conformation called the boat is shown in Eigure 3 14 Like the chair the boat conformation has bond angles that are approximately tetrahedral and is relatively free of angle strain It is however destabi hzed by the torsional strain associated with eclipsed bonds on four of its carbons The... 

At one time all cycloalkanes were believed to be planar It was expected that cyclopentane would be the least strained cycloalkane because the angles of a regular pentagon (108°) are closest to the tetrahedral angle of 109 5° Heats of combustion established that this is not so With the exception of cyclopropane the rings of all cycloalkanes are nonplanar... 

Cyclopropane is planar and destabilized by angle strain and torsional strain Cyclobutane is nonplanar and less strained than cyclopropane... 

Cyclopentane has two nonplanar conformations that are of similar sta bility the envelope and the half chair... 

Structural studies show allene to be nonplanar As Figure 10 7 illustrates the plane of one HCH unit is perpendicular to the plane of the other Figure 10 7 also portrays the reason for the molecular geometry of allene The 2p orbital of each of the terminal car bons overlaps with a different 2p orbital of the central carbon Because the 2p orbitals of the central carbon are perpendicular to each other the perpendicular nature of the two HCH units follows naturally... 

The nonplanarity of allenes has an interesting stereochemical consequence 1 3 Disubstituted allenes are chiral they are not superimposable on their mirror images Even an allene as simple as 2 3 pentadiene (CH3CH=C=CHCH3) has been obtained as sep arate enantiomers... 

A second isomer of [lOJannulene (the cis trans cis cis trans stereoisomer) can have bond angles close to 120° but is destabilized by a close contact between two hydro gens directed toward the interior of the ring To minimize the van der Waals strain between these hydrogens the nng adopts a nonplanar geometry which limits its ability to be stabilized by tt electron delocalization It too has been prepared and is not very stable Similarly the next higher (4n + 2) system [14]annulene is also somewhat desta bilized by van der Waals strain and is nonplanar... 

As noted earlier planar annulenes with 4n tt electrons are antiaromatic A mem ber of this group [16]annulene has been prepared It is nonplanar and shows a pattern of alternating short (average 134 pm) and long (average 146 pm) bonds typical of a nonaromatic cyclic polyene... 

Cyclobutane has less angle strain than cyclopropane (only 19.5°). It is also believed to have some bent-bond character associated with the carbon-carbon bonds. The molecule exists in a nonplanar conformation in order to minimize hydrogen-hydrogen eclipsing strain. 

Cyclopentane is nonplanar, with a structure that resembles an envelope (see Fig. 1.5). Four of the carbon atoms are in one plane, and the fifth is out of that plane. The molecule is in continual motion so that the out-of-plane carbon moves rapidly around the ring. 

The plasma source implantation system does not use the extraction and acceleration scheme found in traditional mass-analy2ing implanters, but rather the sample to be implanted is placed inside a plasma (Fig. 4). This ion implantation scheme evolved from work on controlled fusion devices. The sample is repetitively pulsed at high negative voltages (around 100 kV) to envelope the surface with a flux of energetic plasma ions. Because the plasma surrounds the sample, and because the ions are accelerated normal to the sample surface, plasma-source implantation occurs over the entire surface, thereby eliminating the need to manipulate nonplanar samples in front of the ion beam. In this article, ion implantation systems that implant all surfaces simultaneously are referred to as omnidirectional systems. 

Conformation. The exact conformation of the isoprene molecule is stiU in doubt. It is generally accepted that rotation is restricted around the central C—C single bond. Isoprene may be considered as an equiHbrium of two conformations, namely a cisoid s-cis) conformation in which both vinyl groups are located on the same side of the C—C bond, and a transoid s-trans) one with the vinyl groups located on the opposite sides of the bond. The predominance of the trans-planar or nonplanar configuration has been supported by experimental data (10—14). 

Nonplanar metal objects can be clad, eg, the inside of a cylindrical nozzle can be clad with a corrosion-resistant liner. 

In contrast, chromium (ITT) and cobalt(III) form 2 1 dye metal complexes that have nonplanar stmctures. Geometrical isomerism exists. The (9,(9 -dihydroxyazo dyes (22) form the Drew-Pfitzner or y rtype (23) (A = C = O) whereas o-hydroxy—o -carboxyazo dyes (24) form the Pfeiffer-Schetty or fac type (25), where A = CO 2 and C = O. 

One drawback of systems shown in Fig. 3.1 is that the initial peak shock pressure on the specimen is limited and not well sustained. It immediately starts to decrease, which leads to an attenuation of the shock front as it propagates through the specimen. Attenuation of the shock is detrimental to the accuracy of the resulting experimental data. Also, the late-time release of pressure at the specimen surface is nonplanar, which rules out obtaining accurate information on the specimen s unloading behavior. 

Cyclopentane is nonplanar, and the two minimum-energy geometries are the envelope and half-chair. In the envelope conformation, one carbon atom is displaced from the plane of the other four. In the half-chair conformation, three carbons are coplanar, vdth one of the remaining two being above the plane and the other below. The energy differences between the conformers are very small, and interconversion is rapid. All of the carbon atoms r idly move through planar and nonplanar positions. The process is called pseudorotation. 

The Hiickel rule predicts aromaticity for the six-7c-electron cation derived from cycloheptatriene by hydride abstraction and antiaromaticity for the planar eight-rc-electron anion that would be formed by deprotonation. The cation is indeed very stable, with a P Cr+ of -1-4.7. ° Salts containing the cation can be isolated as a product of a variety of preparative procedures. On the other hand, the pK of cycloheptatriene has been estimated at 36. ° This value is similar to those of normal 1,4-dienes and does not indicate strong destabilization. Thus, the seven-membered eight-rc-electron anion is probably nonplanar. This would be similar to the situation in the nonplanar eight-rc-electron hydrocarbon, cyclooctatetraene. 

---