Conformational dynamics of tetraisopropylmethane and of tetracyclopropylmethane.
Tetraisopropylmethane (1) exists in solution as a mixture of two types of conformers (D2d and S4 time-averaged symmetry) in the ratio 93:7 at -110 degrees C, interconverting with a barrier of 9.7 kcal mol-1. Molecular mechanics calculations and the multiplicity of NMR signals at low temperature allow the assignment of these conformations. The only conformation populated in tetracyclopropylmethane (2) is the same type as the minor conformation (S4 time-averaged symmetry) populated in 1. 13C NMR spectra at about -180 degrees C show that degenerate versions of this conformation interconvert with a barrier of 4.5 kcal mol-1. Molecular mechanics calculations that characterize the six possible conformational types for these molecules, and the most important interconversion pathways, are reported. Calculated and experimental barriers match satisfactorily well.
Anderson
J Edgar
JE
Chemistry Department, University College, Gower Street, London, WC1E 6BT, UK. j.e.anderson@ucl.ac.uk
De Meijere
Armin
A
Kozhushkov
Sergei I
SI
Lunazzi
Lodovico
L
Mazzanti
Andrea
A