Electron groups repulsion between

Polar effects appear to be important for 3 -alkoxy substituents in enolates. 3-Benzyloxy groups enhance the facial selectivity of /(-boron enolates, and this is attributed to a TS I in which the benzyloxy group faces toward the approaching aldehyde. This structure is thought to be preferable to an alternate conformation J, which may be destabilized by electron pair repulsions between the benzyloxy oxygen and the enolate oxygen.109... 

When two, three, four, five, or six objects attached to a central point maximize the space between them, five geometric patterns result, which Figure 10.2A shows with balloons. If the objects are valence-electron groups, repulsions maximize the space each occupies around the central atom, and we obtain the five electron-group arrangements seen in the great majority of molecules and polyatomic ions. 

Crystal structure analysis of 43 revealed that the radical is perfectly trigonal planar, implying the sp -hybridization of the central Si atom and, hence, the localization of the unpaired electron on its 3pz-orbital. The remarkable planarity of the radical 43 was explained by the great steric bulk of the voluminous t-Bu2MeSi groups, which prefered to move away from each other as far as possible to avoid the steric repulsion between them. On the contrary, the significant electron donation of the positive silyl substituents... 

Nucleic acids, DNA and RNA, are attractive biopolymers that can be used for biomedical applications [175,176], nanostructure fabrication [177,178], computing [179,180], and materials for electron-conduction [181,182]. Immobilization of DNA and RNA in well-defined nanostructures would be one of the most unique subjects in current nanotechnology. Unfortunately, a silica surface cannot usually adsorb duplex DNA in aqueous solution due to the electrostatic repulsion between the silica surface and polyanionic DNA. However, Fujiwara et al. recently found that duplex DNA in protonated phosphoric acid form can adsorb on mesoporous silicates, even in low-salt aqueous solution [183]. The DNA adsorption behavior depended much on the pore size of the mesoporous silica. Plausible models of DNA accommodation in mesopore silica channels are depicted in Figure 4.20. Inclusion of duplex DNA in mesoporous silicates with larger pores, around 3.8 nm diameter, would be accompanied by the formation of four water monolayers on the silica surface of the mesoporous inner channel (Figure 4.20A), where sufficient quantities of Si—OH groups remained after solvent extraction of the template (not by calcination). 

In general, type II compounds show greater NO-releasing ability than type I N-nitrosamines. This can be explained by the electronic repulsion between the carbonyl oxygen and nitroso oxygen, or the attraction of the lone-pair electrons at nitrogen, by the carbonyl group both features weaken the N-NO bond. 

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