title: The "hockey sticks" effect revisited: the conformational and electronic properties of 3,7-dithia-1,5-diazabicyclo[3.3.1]nonane from the QTAIM perspective.
abstract: The conformational effects in bicyclo[3.3.1]nonanes, while thoroughly studied, have not yet received the full theoretical explanation. R. F. W. Bader's quantum theory of atoms in molecules presents unique opportunities for studying the stereoelectronic interactions (SEI) and weak intramolecular bonding leading to these effects. Here, we report the study of 3,7-dithia-1,5-diazabicyclo[3.3.1]nonane by means of the topological analysis of the calculated (MP2(full)/6-311++G**) and experimental (X-ray derived) charge density to reveal the origins of the so-called "hockey sticks" effect observed in similar compounds. A new explanation of the relative stability of bicyclo[3.3.1]nonane conformers based on the analysis of the QTAIM atomic energies is given. The H···H and S···S interactions in bicyclo[3.3.1]nonane and its dithia derivatives are shown to be significant factors contributing to the differences in the relative stability of the conformers.
authors: AN Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia.
authors: I S
authors: IS
authors: Bushmarinov
authors: I V
authors: IV
authors: Fedyanin
authors: K A
authors: KA
authors: Lyssenko
authors: V L
authors: VL
authors: Lapteva
authors: S A
authors: SA
authors: Pisarev
authors: V A
authors: VA
authors: Palyulin
authors: N S
authors: NS
authors: Zefirov
authors: M Yu
authors: MY
authors: Antipin
mesh_terms: D053961:Azabicyclo Compounds / Q000737:chemistry*; D004583:Electrons; D008968:Molecular Conformation; D011789:Quantum Theory
chemical_list: D053961:Azabicyclo Compounds