Dramatic differences in the conformational equilibria of chalcogen-bridged compounds: the case of diallyl ether versus diallyl sulfide

Abstract

The conformational landscapes of diallyl ether (DAE) and diallyl sulfide (DAS) were investigated for the first time using rotational spectroscopy from 6–20 GHz supported by quantum mechanical calculations. A significant difference in the conformational distribution of these chalcogen-bridged compounds is predicted by theory at the B3LYP-D3(BJ)/aug-cc-pVTZ level as DAS has only one low energy conformer while DAE has up to 12 energy minima within 5 kJ mol⁻¹. This was confirmed by rotational spectroscopy as only transitions corresponding to the global minimum of DAS were observed while the spectrum of DAE was much richer and composed of features from the nine lowest energy conformers. To understand the effects that govern the conformational preferences of DAE and DAS, natural bond orbital and non-covalent interaction analyses were done. These show that unique orbital interactions stabilize several conformers of the ether making its conformational landscape more competitive than that of the sulfide. This is consistent with a bonding model involving decreased hybridization of the bridging atom as one moves down the periodic table which is confirmed by the experimental ground state structures of the lowest energy forms of DAE and DAS, derived using spectra of the ¹³C and ³⁴S substituted species in natural abundance.