Inverse hydrogen bonds between SiH4 and hydrides of Na, Mg and Be

Abstract

The optimized geometries of the three complexes between MeH n (Me=Na, Mg, Be; n=1 or 2) and SiH 4 have been calculated at the B3LYP/6-311++g**, MP2/6-311++g(3df,3pd) and MP2/aug-cc-pvtz levels, respectively. The red-shift inverse hydrogen bonds (IHBs) based on Si-H, an electron donor, were reported. The calculated binding energies with basis set super-position error (BSSE) correction of the three complexes are 5.98, 8.65 and 3.96 kJ mol 1 (MP2/6-311++g(3df, 3pd)), respectively, which agree with the results obtained via MP2/aug-cc-pvtz (6.18, 9.12 and 4.28 kJ mol 1 , respectively). The relative stabilities of the three complexes are in the order of SiH 4 ···MgH 2 > SiH 4 ···NaH > SiH 4 ···BeH 2 . Natural bond orbital theory (NBO) analysis and the chemical shift calculation of the related atoms revealed that the charges flow from SiH 4 to MeH n and the chemical shifts of the interacting H shift to downfield. Here, the Si1-H3 of SiH 4 acts as both a bond hydrogen donor and an electron donor. Therefore, compared with conventional hydrogen bonds, they formed IHB complexes. Atoms in molecules (AIM) theory have been used to investigate the topological properties of the critical points in the three IHB structures.SiH 4 , metal hydride, inverse hydrogen bond, electron density topological property

A study of cation-dependent inverse hydrogen bonds and magnetic exchange-couplings in lanthanacarborane complexes

“…IHB was initially proposed by Rozas et al, in 1997 when investigating the intermolecular interactions in metal hydrides due to the electronegativity of the hydrogen atom is much stronger than many metal atoms (Rozas, et al, 1997). Later, the IHBs were also found in nonmetal hydrides, such as SiH 4 and XeH 2 (Blanco et al, 2008;Yuan, et al, 2011). But as a whole, IHBs are still very scarce due to lower electron affinity of the hydrogen atom in most of the X-H bonds.…”