On the Structure of Boat-Shaped Hexalead(II) Cations with OH Bridges

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Title:On the Structure of Boat-Shaped Hexalead(II) Cations with OH Bridges
Creators:
Breza, Martin
Biskupič, Stanislav
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 69, 11, pp. 2055-2067
Uncontrolled Keywords:<i>Ab initio</i> calculations, Geometry optimizations, Lead(II) clusters, Hydroxo complexes, Molecular structure

Abstract

Using Hartree-Fock, B3LYP, and MP2 treatments, the optimal boat-shaped geometries and corresponding electronic structures of [Pb<sub>6</sub>O<i><sub>m</sub></i>(μ<sub>3</sub>-OH)<i><sub>n</sub></i>]<i><sup>q</sup></i> complex cations with total charges <i>q</i> = 12 - 2<i>m</i> - <i>n</i>, <i>m</i> = 0 or 1, <i>n</i> = 6 or 8, are investigated. Whereas the [Pb<sub>6</sub>(μ<sub>3</sub>-OH)<sub>6</sub>]<sup>6+</sup> cation is unstable, the remaining structures preserve <i>C</i><sub>2v</sub> symmetry. Direct Pb-Pb interactions are weakly antibonding in all the systems under study. The clusters are held together exclusively by relatively weak Pb-O bonds. The effects of central O and two additional μ<sub>3</sub>-OH bridges in [Pb<sub>6</sub>O(μ<sub>3</sub>-OH)<sub>8</sub>]<sup>2+</sup> are not fully cooperative. [Pb<sub>6</sub>O(μ<sub>3</sub>-OH)<sub>6</sub>]<sup>4+</sup> and [Pb<sub>6</sub>(μ<sub>3</sub>-OH)<sub>8</sub>]<sup>4+</sup> may coexist in water solutions in comparable concentrations. <p>

Title:On the Structure of Boat-Shaped Hexalead(II) Cations with OH Bridges
Creators:
Breza, Martin
Biskupič, Stanislav
Uncontrolled Keywords:<i>Ab initio</i> calculations, Geometry optimizations, Lead(II) clusters, Hydroxo complexes, Molecular structure
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:69
Number:11
Page Range:pp. 2055-2067
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20042055UNSPECIFIED
ID Code:2320
Item Type:Article
Deposited On:06 Feb 2009 17:17
Last Modified:06 Feb 2009 16:17

Citation

Breza, Martin; Biskupič, Stanislav (2004) On the Structure of Boat-Shaped Hexalead(II) Cations with OH Bridges. Collection of Czechoslovak Chemical Communications, 69 (11). pp. 2055-2067. ISSN 0010-0765

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