Model quartets

Qiana, structure of, 836 Quantum mechanical model, 4-6 Quartet (NMR), 460 Quaternary ammonium salt. 917 Hofmann elimination and, 936-937... 

Recently, Switzer and co-workers have further extended the multi-stranded motifs for nucleic acids with the formation of a quintet assembly with oligonucleotides containing 2,deoxy-iso-guanosine (74). To support the quintet, metal ions larger than those appropriate for quartet stabilization were required, and Cs+ ions were found to best meet this requirement. From modeling studies, a structure in which a central Cs+ interacts with ten 02 iG atoms at a distance of 3.5 A was proposed. 

Linnett used the concept that an octet of valence shell electrons consists of two sets of four opposite-spin electrons to show that in diatomic and other linear molecules the two tetrahedra are not in general formed into four pairs as we have discussed for F2 and the CC triple bond in C2H2. This idea is the basis of the double-quartet model, which Linnett applied to describe the bonding in a variety of molecules. It is particularly useful for the description of the bonding in radicals, including in particular the oxygen molecule, which has two unpaired electrons and is therefore paramagnetic This unusual property is not explained by the Lewis structure... 

Thus there are five bonding electrons giving a bond order of 2.5, consistent with the bond length of 115 pm, versus 121 pm for the four-electron bond in O2 and 110 pm for the six-electron bond in N2. For these and other related molecules, the double-quartet model is a convenient and useful alternative to the conventional molecular orbital model. Moreover, it shows that for a singly bonded terminal atom such as F or Cl there is a ring of six nonbonding electrons rather than three separate lone pairs. As we will see in Chapters 7 and 8, this conclusion is confirmed by the analysis of electron density distributions. 

Different balance between intermolecular forces can be accessible via partition coefficients measured in solvents systems other than the traditional 1-octanol/water. Therefore there was a growing interest in the partition processes in several solvent/ water systems [64, 65] and in particular the critical quartet of solvents which was designed to merge the main information about a solute concerning its partition and transport. Only a few studies have been performed to characterize the lipophilicity profile of new chemical entities in different solvent/water systems and consequently the number of methods attempting to model such partitioning systems is limited. 

Leahy, D., J.J. Morris, and P.J. Taylor. 1992. Model Solvent Systems for QSAR. Part 3. An LSER Analysis of the "Critical Quartet " New Light on Hydrogen Bond Strength and Directionality. /. Chem. Soc. Perkin Trans. 2, 705-731. 

Williamson, J. R., Raghuraman, M. K., Cecil, T. R., Mono valent cation induced structure of telomeric DNA - the G-quartet model. Ceil 1989, 59, 871-880. 

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