Collect. Czech. Chem. Commun. 2004, 69, 2045-2054

On the Structure of Tetralead(II) Complexes with OH Bridges

Martin Breza* and Stanislav Biskupič

Department of Physical Chemistry, Slovak Technical University, SK-812 37 Bratislava, Slovakia


Using Hartree-Fock, B3LYP and MP2 treatments, the optimal geometries and corresponding electronic structures of tetrahedral [Pb43-OH)n]q and [Pb4O(μ3-OH)n]q-2 complex cations with total charges q = 8 - n , n = 2, 3, 4, are investigated. After OH- removal, the central oxygen atom in [Pb4O(μ3-OH)4]2+ is shifted to the apical position in [Pb4O(μ3-OH)3]3+ whereas the [Pb43-OH)2]6+ and [Pb4O(μ3-OH)2]4+ complex cations are unstable. Direct Pb-Pb and O-O interactions are weakly antibonding in all the systems under study. The clusters are held together exclusively by relatively weak Pb-O bonds. A higher stability of the complex cations with a larger number of OH- bridges may be confirmed.

Keywords: Lead(II) clusters; Hydroxo complexes; Molecular structure; Geometry optimizations; Ab initio calculations; DFT.

References: 56 live references.