Beryllium Bonds, Do They Exist?
Citations Over TimeTop 10% of 2009 papers
Abstract
The complexes between BeX2 (X = H, F, Cl, OH) with different Lewis bases have been investigated through the use of B3LYP, MP2, and CCSD(T) approaches. This theoretical survey showed that these complexes are stabilized through the interaction between the Be atom and the basic center of the base, which are characterized by electron densities at the corresponding bond critical points larger than those found in conventional hydrogen bonds (HBs). Actually, all bonding indices indicate that, although these interactions that we named "beryllium bonds" are in general significantly stronger than HBs, they share many common features. Both interactions have a dominant electrostatic character but also some covalent contributions associated with a non-negligible electron transfer between the interacting subunits. This electron transfer, which in HBs takes place from the HB acceptor lone-pairs toward the σYH* antibonding orbital of the HB donor, in beryllium bonds goes from the lone pairs of the Lewis base toward the empty p orbital of Be and the σBeX* antibonding orbital. Accordingly, a significant distortion of the BeX2 subunit, which in the complex becomes nonlinear, takes place. Concomitantly, a significant red-shifting of the X-Be-X antisymmetric stretching frequencies and a significant lengthening of the X-Be bonds occur. The presence of the beryllium bond results in a significant blue-shifting of the X-Be-X symmetric stretch.
Related Papers
- → Molecular Orbitals of the Oxocarbons (CO)n, n = 2–6. Why Does (CO)4 Have a Triplet Ground State?(2012)48 cited
- → Can One σ*-Antibonding Orbital Interact with Six Electrons of Lewis Bases? Analysis of a Multiply Interacting σ* Orbital(2014)14 cited
- → Thallium Halides — New Aspects of the Stereochemical Activity of Electron Lone Pairs of Heavier Main‐Group Elements(2007)1 cited
- → Some Electron-Excess σ Bonded Systems(2015)
- → Some Electron-Excess σ Bonded Systems(1982)