Conformational energies, additivity

Additionally, it was found that the energy difference between the two transition states (3 and 4) is determined mainly by the difference in the conformational energy of the a-chloro aldehyde in the two transition states i.e., the energetic preference of transition state 3 over 4 is due to a more favorable conformation of the aldehyde rather than a more favorable interaction with the attacking nucleophile. In fact, interaction between lithium hydride and 2-chloropropanal stabilizes transition state 4, which yields the minor diastereomer. 

Use of Rh2(OAc)4 suggested that there was no inherent selectivity attributable to the coordinated carbene or to rhodium(ll). However, modification of dirhodium(ll) ligands to imidazolidinones provided exceptional diastereocontrol, obtained by influencing the conformational energies of the intermediate metal carbene [19, 23], as well as high enantiocontrol. Representative examples of products from these highly selective intramolecular C-H insertion reactions with cyclic systems is given in Scheme 15.6. Additional examples of effective insertions in systems from which diastereomeric products can result are illustrated in processes of the synthesis of 2-deoxyxylolactone (Scheme 15.7) [64, 65]. Here the conformation of the reactant metal carbene that is responsible for product formation is 32 rather than 33. Other examples in non-heteroatom-bound systems (for example, as in Eq. 15) confirm this preference. 

These potential energy terms and their attendant empirical parameters define the force field (FF). More complicated FFs which use different and/or more complex functional forms are also possible. For example, the simple harmonic oscillator expression for bond stretching can be replaced by a Morse function, Euorse (3), or additional FF terms may be added such as the stretch-bend cross terms, Estb, (4) used in the Merck molecular force field (MMFF) (7-10) which may be useful for better describing vibrations and conformational energies. 

Approximate conformational energy estimates are utilized to evaluate the RIS model of PVDF, Occasional 10-20%) head to head tail to tail (H-H T-T) addition of monomer units in a random fashion is accounted for In the calculation of these conformational properties. In general it is found that the calculated conformational properties are relatively insensitive to the amount of H-H T-T addition assumed, but are instead markedly dependent upon the value of the dielectric constant Is) selected to mediate the electrostatic interactions encountered along a PVDF chain. 

For POM, a matrix algorithm for the statistical mechanical treatment of an unperturbed -A-B-A-B- polymer chain with energy correlation between first-neighboring skeletal rotations is described. The results of the unperturbed dimensions are in satisfactory agreement with experimental data. In addition, if the same energy data are used, the results are rather close to those obtained by the RIS scheme usually adopted. The RIS scheme is shown to be also adequate for the calculation of the average intramolecular conformational energy, if the torsional oscillation about skeletal bonds is taken into account in the harmonic approximation. 

Dielectric constants are determined for pure liquid dimethylsiloxane oligomers. Mean-square dipole moments, calculated from the Onsager equation, are in good agreement with predicted values based on the RIS model (S 117) with neighbor dependence and chain conformational energies obtained in an independent analysis of the random-coil dimensions of such chains. In addition, the observed temperature coefficients of are in qualitative agreement with calculated results. 

The helical parameters corresponding to the various skeletal conformations of the blsphenol A polycarbonate chain are calculated. Combining these results with the conformational energy calculations shows that flat-helical and extended conformations are of equal energy for this chain. In addition, cyclic structures are also found to be stereochemically possible. The small values of the characteristic ratio of the unperturbed end-to-end distance and its temperature coefficient are attributed to the equal energy of the flat-helical and extended-helical, as well as the nonhelical, conformers. 

Mean-square unperturbed dimensions a and their temperature coefficient, d tin 0) I d T, are calculated for ethylene-propylene copolymers by means of the RIS theory. Conformational energies required in the analysis are shown to be readily obtained from previous analyses of PE and PP, without additional approximations. Results thus calculated are reported as a function of chemical composition, chemical sequence distribution, and stereochemical composition of the PP sequences. Calculations of 0 / nP- are earned out using ( ) r r2 = 0.01, 1.0, 10.0, and 100.0, (ii) p, = 0.95, 0.50, and 0.05, liii) bond length of 153 pm and bond angles of 112°for all skeletal bonds, iv) = 0 and 10°, and (v) statistical weight factors appropriate for temperatures of 248, 298, and 348 K. Matrices used are ... 

H - H interactions, both for all-(S) and (R,R,S,S) tetramers, even after conformational energy minimisation. Overall, most of the >40 kcal mol-1 enthalpic advantage of the [dimer + dimer to tetramer] process is lost on going from methylzinc to isopropylzinc-derived structures, because of the increased steric strain. The remaining [Zn-Oh square-based tetramers are all more strained in the isopropyl than in the Me series. As an extreme, the latter is less stable than two isolated monomers. What stands out is that the square-capped macrocycle is only modestly more strained in the isopropyl series, and lacks severe H - H interactions (only two H - H contacts are below 2.3 A). Forming the barrel isomer from this by making two additional Zn - N... 

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