title: Gas-phase structure and conformational properties of 3,3,6,6-tetramethyl-1,2,4,5-tetroxane.
abstract: The geometric structure and conformational properties of 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (diacetone diperoxide) have been studied by gas electron diffraction and quantum chemical calculations (MP2 and B3LYP methods with 6-31G(d,p) and 6-311+G(2df,p) basis sets). The molecule possesses a chair conformation with C2h symmetry and the following geometric parameters for the six-membered ring (rh1 values) have been determined: O-O = 1.463(5) A, C-O = 1.432 (4) A, O-C-O = 108.2(7) degrees, C-O-O = 107.7(4) degrees, phi(C-O-O-C) = 63.7(4) degrees, and phi(O-O-C-O) = -63.9(4) degrees. A small contribution of less than 3.5% of a twist conformer with C2 symmetry cannot be excluded. Quantum chemical calculations predict a contribution between 1 and 2%. Additional calculations for the parent compound 1,2,4,5-tetroxane (diformaldehyde diperoxide) demonstrate that methyl substitution at the carbon atoms has a minor effect on the ring geometry but a strong effect on the conformational properties. Methyl substitution reduces the energy difference between twist and chair conformers by more than 5 kcal/mol.
authors.affiliation: Department of Physics, Ivanovo State University of Chemical Technology, Engels av. 7, 153 000 Ivanovo, Russia. shlykov@isuct.ru
authors.forename: Sergey A
authors.initials: SA
authors.lastname: Shlykov
authors.forename: Nina I
authors.initials: NI
authors.lastname: Giricheva
authors.forename: Gladys N
authors.initials: GN
authors.lastname: Eyler
authors.forename: Heinz
authors.initials: H
authors.lastname: Oberhammer