title: Helical chirality in hexamethylene triperoxide diamine.
abstract: The primary explosive hexamethylenetriperoxide diamine has previously been found to exist in the solid state as a racemic mixture of helically chiral, threefold symmetric enantiomers; another enantiomeric pair of low-energy conformers has been predicted, but has never been observed. We show by solution 2D NMR at 14 T, in achiral solution and by addition of chiral shift reagents, that all four optically isomeric conformers coexist at slow equilibrium on the NMR timescale at room temperature, and can be observed. Calculations of the 1H and 13C NMR chemical shifts using gauge-including atomic orbital methods are in excellent agreement with experiment; thermochemical calculation of the free energies in solution are in somewhat worse agreement, but correctly predict the relative stability of the conformers. Analysis of the effects of chiral shift reagents on the NMR spectra suggests that discrimination between chiral isomers is primarily around the molecular equator, around which the enantiomeric gauche O--O linkages are arrayed.
authors.affiliation: Department of Chemistry, University of Nebraska at Lincoln, Lincoln, NE 68588-0304, USA.
authors.forename: Chunlei
authors.initials: C
authors.lastname: Guo
authors.forename: John
authors.initials: J
authors.lastname: Persons
authors.forename: Gerard S
authors.initials: GS
authors.lastname: Harbison
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D002247:Carbon Isotopes / Q000032:analysis; D053834:Explosive Agents / Q000737:chemistry*; D006859:Hydrogen / Q000032:analysis; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D012996:Solutions / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D002247:Carbon Isotopes; D053834:Explosive Agents; D012996:Solutions; C058103:hexamethylenetriperoxidediamine; D006859:Hydrogen