Hydrogen versus tetrel bonds in complexes of 3-oxetanone with water and formaldehyde

Abstract

The ability and preference of 3-oxetanone to form hydrogen or tetrel bonds have been investigated in its complexes with water and formaldehyde by using Fourier transform microwave spectroscopy complemented with quantum chemical calculations. Different types of interactions and internal dynamics have been observed in the targeted complexes. With water, the ether oxygen of 3-oxetanone is the favoured interaction site forming a classical O–H⋯O hydrogen bond. Quite differently, the carbonyl group of 3-oxetanone plays the dual role as a tetrel donor and a proton acceptor in the 3-oxetanone-formaldehyde complex, featuring the C⋯O tetrel bond and C–H⋯O weak hydrogen bond interactions. Splittings originated from the internal rotation of formaldehyde around its C₂ axis were also observed. The V₂ barrier was estimated to be 375(10) cm⁻¹ based on Meyer's one-dimensional flexible model. The changes in geometries and electronic densities upon complexation would shed light on the impact of archetype solvent and organic substrate molecules on the reactivity of 3-oxetanone.