Changing Weak Halogen Bonds into Strong Ones through Cooperativity with Beryllium Bonds

Abstract

The mutual interaction between beryllium bonds and halogen bonds within H2Be···FCl···Base complexes, where Base includes a wide set of N- and O-containing Lewis bases, has been studied at the M06-2X/6-31+G(d,p) level of theory. The reliability of this theoretical model was assessed by comparison with ab initio CCSD/aug-cc-pVTZ reference calculations. Cooperative effects were investigated within the framework of the atoms in molecules theory (AIM) by analyzing the topology of the electron density and the changes in the atomic energy components. The decomposition of the total stabilization energy into atomic components is found to be a very reliable tool to describe halogen bond interactions. Both the topological analysis of the electron density and the changes in the atomic energy components of the binding energy show the existence of strong cooperative effects between beryllium and halogen bonds, which are in some cases very intense. In general, there is a correlation between the intrinsic basicity of the Lewis base participating in the halogen bond and the resulting cooperativity in the sense that the stronger the base, the larger the cooperative effects.

Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds

“…Spin-spin coupling constants were evaluated using the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method in the CI(configuration interaction)-like approximation, 42,43 with all electrons correlated. For these calculations, the Ahlrichs 44 qzp basis set was placed on 13 C, 15 N, and 19 F, and the qz2p basis set on 35 Cl. A basis set for 9 Be was developed using the same approach as used previously for 7 Li and 11 B.…”

Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH3, CF3) Complexes

“…In the last decade, these interactions have been widely investigated. [1][2][3][4][5] Recently,avariety of speciesi nw hich as ingle, simple Lewisb ase molecule (B, such as CO, N 2 ,H 2 O, H 2 S, C 2 H 2 ,orC 2 H 4 )coordinates to aneutral coinage metal diatomic MÀX( i.e. B···MÀX, in which Mi sC u, Ag, or Au;Xi sahalogen atom) have been investigated widely both theoretically and experimentally.…”

“…They found that significant charge was transferred from the lone-pair donors (HF,H 2 O) to AuOH upon complex formation,s imilart ot hat in hydrogenbondedc omplexes.A dditionally,t wo simple complexes, H 2 O···AgÀCl and H 2 S···AgÀCl, were experimentally characterized by Legon et al [12] Considering the corresponding hydrogenbondeds ystems, they suggested that there was as ilver bond, analogoust ot he more familiarh ydrogen bond. Soon afterwards, [19] our computational studies on H 2 O···AgÀCl and H 2 S···AgÀCl showed that hyperconjugation interactions participated in Ag bonding. This was similart ot hat of hydrogenbondedc omplexes,i nw hich charget ransfer also occurred throughh yperconjugation interactions.…”

“…Herein, we study further extensions of the simple two-resonance "bond order conservation" concept, ase xemplifiedb y[ Eqs. (2) and (3)]. …”

Interplay of Hydrogen, Halogen, Lithium and Beryllium Bonds in Complexes of Thiirane

“…The mutual influence between beryllium bonds and other non-covalent bonds has also been investigated in recent years [105][106][107], though not as extensively as the preceding interactions. Mó et al carried out investigations on the effect of beryllium bonds on inter-and intra-hydrogen bonds [107].…”