Department of Inorganic Chemistry, Charles University, Faculty of Science, Hlavova 2030, 128 40 Prague 2, Czech Republic

摘要

Using Hartree-Fock, B3LYP and MP2 treatments, the optimal geometries and corresponding electronic structures of tetrahedral [Pb4(n.3-OH)n]? and [Pb4O(|mu3-OH)n]?~2 complex cations with total charges q = 8 - n , n = 1, 3, 4, are investigated. After OH~ removal, the central oxygen atom in [Pb4O(ii3-OH)4]2+ is shifted to the apical position in [Pb4O((a3-OH)3]3+ whereas the [Pb4(nrOH)2]6+ and [Pb4O(n3-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.