Strain torsional angle deformation

The simple cycloalkanes (CH2)n with n = 5 to 12 are the compounds most frequently studied by force field calculations (8, 9, 11, 12,17, 21). This preference results from their simple structure, from the abundant available experimental material (structural (46), thermo-chemical (47) and vibrational spectroscopic (27, 48, 49) data), and from the fact that, apart from bond length deformations, all other strain factors (angle deformations, unfavourable torsion angles, strongly repulsive nonbonded interactions) are important for the calculation of their properties. The cycloalkanes are thus good candidates for testing force fields. For a more detailed discussion we choose cyclodecane, a so-called medium-ring compound. 

The rubidium and cesium complexes of [2.2.2] are isomorphous with approximate D3 symmetry and a crystallographic twofold rotation axis (41). While the rubidium cation is complexed almost without strain, the Cs+ is accommodated only by enlarging the cavity, increasing the mean C—C torsion angle to 71° (compared with 54° for the potassium cryptate). The ligand deformations required to complex Na+ and Cs + are reflected in their lower solution stability constants with respect to the K+ and Rb+ cryptates (see Section III,D). 

The thermal reaction, at room temperature, of A -bicyclo[2A0]hexene (277) gave, besides polymeric material, a dimer now identified as 2,5-dimethylenetricyclo-[4,2,2,0 ]decane (278). Reaction of (277) with irons, frans-dimethyl-2,5-hexadiene gave the olefin (279) and reduction of both (278) and (279) gave cis-2,5-dimethyltri-cyclo[4,2,2,0 ]decane. The reactive double bond in (277) differs from that usually associated with thermal olefin dimerizations. In most cases, such reactivity has been associated with double bonds which are torsionally strained. In (277) the torsion angle about the double bond must be zero and the reactivity must be associated with angular deformation at the olefinic carbons. Addition of ketene to (277) gave 3-methyl-6-methylenecyclohex-2-ene-l-one. In both reaction with ketene and dimerization, [2,2,2]propellanes would appear to be reasonable intermediates. 

The absence of significant change in the distribution of the backbone dihedral angles upon plastic deformation of glassy BPA-PC has been experimentally observed. Utz [30] and Utz et al. [31] compressed specifically labeled samples uniaxially and in plane strain to strains of —0.68 and found, by solid-state NMR, that the distributions of the torsion angle pairs (f>2 and (f>4 (or and (f>s) do not change perceptibly. 

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