Abstract
The local electronic structure of the Al=Al bond was studied in dialumene and derivatives of dialumene in which the Al atoms were substituted by B, Ga, or In atoms. DFT calculations were performed using the B3LYP, B3PW91, PBE0, M06-L, and M06-2X functionals. Topological analysis of the electron localization function described the covalent bonds mentioned above using the disynaptic basins Vi=1,2(B,B), Vi=1,2(Al,Al), V(Ga,Ga), and Vi=1,2(In,In). The basin populations were smaller than 4 e, as expected for a double bond: B=B 2.97 e, Al=Al 3.44–3.5 e, Ga=Ga 3.58 e, and In=In 3.86 e. The Al=Al, Ga=Ga, and In=In bonds were found to be intermediate in character between single and double bonds. Topological analysis of the ρ(r) field for dialumene showed a non-nuclear attractor along the Al=Al bond, with a pseudoatom basin population of 0.937 e. NBO analysis suggested that a double bond occurred only in the molecules containing Al, Ga, or In atoms. The character of the Ga=Ga bond was observed to be strongly dependent on the effective core potential used in the calculations.
Highlights
Boron-containing compounds have fascinated researchers over the years [1,2,3,4], but research into homoatomic multiply bonded compounds has been fairly limited
The work reported in the current paper focused on the local nature of the homoatomic Al=Al bond in neutral dialumene
Dialumene derivatives in which the Al atoms were substituted by B, Ga, and In atoms were optimized at the DFT(M06-L)/6-311++G(d,p) level
Summary
Boron-containing compounds have fascinated researchers over the years [1,2,3,4], but research into homoatomic multiply bonded compounds has been fairly limited. The first stable molecule to be found to possess a formal double bond between aluminum atoms (i.e., Al=Al), dialumene, was synthesized and characterized by Bag et al [7] using X-ray crystallographic and 1H NMR analysis (Scheme 1). This molecule possesses a trans-planar geometry in the solid state. The work reported in the current paper focused on the local nature of the homoatomic Al=Al bond in neutral dialumene. The electronic structures of similar homoatomic bonds (B=B, Ga=Ga, and In=In) were investigated in order to establish general trends in the properties of interest. The Cambridge Structural Database (CSD; version 5.39, November 2017 [30]) was used to analyze B–B and Al–Al contacts
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