Cage structure

The reason the adamantyl system is much more sensitive to the substitutions of CH3 for H is that its cage structure prevents solvent participation whereas the i-propyl system has much stronger solvent participation. The internal stabilizing effect of the methyl substituent is therefore more important in the adamantyl system. 

Tiling rule for cage structure of graphitic carbon... 

Cluster and cage structures are widespread in the chemistry of main group elements, being particularly extensive in the case of boron (Chap. 6). For transition elements the principal... 

Not surprisingly, light was soon featured in syntheses of numerous complex molecules. In fact, in 1958, only one year after Biichi s confirmation of Ciamician s discovery, Cookson et al. reported the facility with which complex cage structures (see VII, Scheme 1) can be constructed through intramolecular [2+2] photo-... 

Hydrophobic interactions of this kind have been assumed to originate because the attempt to dissolve the hydrocarbon component causes the development of cage structures of hydrogen-bonded water molecules around the non-polar solute. This increase in the regularity of the solvent would result in an overall reduction in entropy of the system, and therefore is not favoured. Hydrophobic effects of this kind are significant in solutions of all water-soluble polymers except poly(acrylic acid) and poly(acrylamide), where large heats of solution of the polar groups swamp the effect. 

The problem of accessibility in microporous solids is extreme in zero-dimensional zeolite structures such as clathrasils, that is, zeolite-related materials consisting of window-connected cages. The pore openings in these caged structures are restricted to six-membered rings of [Si04] units at most, which corresponds to pore diameters of approximately 0.2 nm [58]. These pores are too small for the removal of templates and, afterward, are impenetrable to typical sorptive molecules for characterization such as N2 and Ar or reactants such as hydrocarbons. Therefore, the intrinsic... 

Li Q, Walter EC, van der Veer WE, Murray BJ, Newberg JT, Bohannan EW, Switzer JA, Hemminger JC, Penner RM (2005) Molybdenum disulfide nanowires and nanoribbons by electrochemical/chemical synthesis. J Phys Chem B 109 3169-3182 Tenne R, Homyonfer M, Feldman Y (1998) Nanoparticles of layered compounds with hollow cage structures (inorganic fuUerene-like structures). Chem Mater 10 3225-3238 Shibahara T (1993) Syntheses of sulphur-bridged molybdenum and tungsten coordination compounds. Coord Chem Rev 123 73-147... 

Heptachlor and cw-chlordane, both of which are chiral, produce caged or half-caged structures (Figure 1.8) on irradiation, and these products have been identified in biota from the Baltic, the Arctic, and the Antarctic (Buser and Muller 1993). 

The most widely exploited photochemical cycloadditions involve irradiation of dienes in which the two double bonds are fairly close and result in formation of polycyclic cage compounds. Some examples of alkene photocyclizations are given in Scheme 6.9. Entry 1 is a transannular cyclization. The preference for the observed product over tricyclo[4.2.0.02,5]octane does not seem to have been analyzed in detail. Entries 2, 3, and 4 involve photolysis in the presence of Cu03SCF3. Entries 5 and 6 are cases in which the double bonds are in close proximity and can cyclize to caged structures. 

The rigidity of the hexacyclic cage structure of koumine (18) renders some of its chemical behavior quite unusual, for instance, the resistance to Hofmann degradation shown by /Va-acetyldihydrokoumine methyl hydroxide (27). However, owing to the presence of a /J-aromatic imino system in 18, reductive cleavage by sodium-alcohol to yield dihydrokouminol (39) proceeds smoothly. This reaction has been considered to occur through a radical-anion mechanism as indicated in Scheme 12 (27). 

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