Orientation-dependent reaction

In the section dealing with electrophilic attack at carbon some results on indazole homocyclic reactivity were presented nitration at position 5 (Section 4.04.2.1.4(ii)), sulfon-ation at position 7 (Section 4.04.2.1.4(iii)) and bromination at positions 5 and 7 (Section 4.04.2.1.4(v)). The orientation depends on the nature (cationic, neutral or anionic) of the indazole. Protonation, for instance, deactivates the heterocycle and directs the attack towards the fused benzene ring. A careful study of the nitration of indazoles at positions 2, 3, 5 or 7 has been published by Habraken (7UOC3084) who described the synthesis of several dinitroindazoles (5,7 5,6 3,5 3,6 3,4 3,7). The kinetics of the nitration of indazole to form the 5-nitro derivative have been determined (72JCS(P2)632). The rate profile at acidities below 90% sulfuric acid shows that the reaction involves the conjugate acid of indazole. 

A number of different techniques have been applied to test the distance and orientation dependence of ET reactions (Closs and Miller, 1988 Closs et al, 1989 Liang et al., 1990 Reimers and Hush, 1990 Fox and Chanon, 1988 Wasielewski, 1989 Paddon Row and Jordan, 1988 Joachim et al, 1990 McConnell, 1961). Our method of analysing the mode of charge distribution in charged species is esr spectroscopy, which defines the timescale of the detectable dynamic species (Gerson, 1967 Kurreck et al, 1988 Wertz and Bolton, 1972). If an electron transfer is slow relative to the esr timescale (<10 7s) the spectrum corresponds to that of monomeric model compounds with a single electrophore. If the hopping process is rapid on the esr timescale, one will detect an effective delocalization. 

The rate of removal of surface silicon atoms by the electrochemical reactions is orientation dependant, lowest on (111) and higher on other orientations. 

In summary, preliminary experiments have demonstrated that the efficiency and outcome of electron ionization is influenced by molecular orientation. That is, the magnitude of the electron impact ionization cross section depends on the spatial orientation of the molecule widi respect to the electron projectile. The ionization efficiency is lowest for electron impact on the negative end of the molecular dipole. In addition, the mass spectrum is orientation-dependent for example, in the ionization of CH3CI the ratio CHjCriCHj depends on the molecular orientation. There are both similarities in and differences between the effect of orientation on electron transfer (as an elementary step in the harpoon mechanism) and electron impact ionization, but there is a substantial effect in both cases. It seems likely that other types of particle interactions, for example, free-radical chemistry and ion-molecule chemistry, may also exhibit a dependence on relative spatial orientation. The information emerging from these studies should contribute one more perspective to our view of particle interactions and eventually to a deeper understanding of complex chemical and biological reaction mechanisms. 

We can also consider a time-dependent reaction field (Eqs. (14) and (15)) which includes an orientational term ROI and an instantaneous (optical) term... 

The orientation dependence of the interface reaction has been attributed to the number of Si-Si bonds available for reaction (76, 106, 107), the orientation of the bonds (76, 106), the presence of surface steps (108, 109), stress in the oxide film (110, 111), and the attainment of maximum coherence across the Si-Si02 interface (76, 111). However, no strong correlations have been established between these properties and oxidation rate, although Lewis and Irene (105) developed a qualitative correlation between the order of the initial rates and the density of atoms on planes parallel to the surface. 

When the donors and acceptors lack spherical symmetry, there will also be an orientation dependence. In cases such as those to be discussed below, where the donor and acceptor moieties are linked by covalent bonds, there is considerable evidence that in certain situations the electron transfer occurs through the linkage bonds [22]. Although such linkages are not present in photosynthetic reaction centers, it has been proposed that the accessory Bchl or other intervening material may still take part in electron transfer through a superexchange mechanism [8, 26]. The distance dependence of photoinitiated electron transfer has recently been reviewed [13]. 

Halohydrins. The reaction of a slight excess of 1, Br, or Cl, and of P(C6H,)j in CH2CI2 with an epoxide results in a halohydrin in generally high yield. The orientation depends in part on the bulkiness of the halide ion, but the halogen ion generally attacks the less substituted carbon atom. 

The photochemical properties of titania surfaces are of interest for several reasons. They determine the stability of pigmented paint systems [76], the rate at which pollutants can be degraded in systems designed to purify air and water [77], and are the root cause of poorly understood phenomena such as water photolysis [78] and super hydrophilicity [79]. Using thin rutile epilayers with five low index orientations, it has been shown that the relative rates of photochemical reactions catalyzed by titania depend on the surface orientation [80]. In this chapter, experiments used to map the complete orientation dependence of the relative photochemical reactivity of TiO are described [81-83]. In this case, the relevant reactions are carried out at room temperature and this gives us the opportunity to fix both the surface morphological structure and stoichiometry. For the reactions described here, all of the surfaces were... 

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