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Synthesis and structural characterisation of the lead–platinum sulfido aggregates [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I); promotion of rare tetrahedral geometry for lead(II)

Abstract
The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with excess PbBr₂ or PbI₂ in methanolic suspension result in the formation of the neutral lead(II) halide adducts [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I). The X-ray structure determination of the lead iodide adduct reveals an essentially tetrahedral lead(II) centre, which is a rare coordination geometry for lead(II), which almost invariably is hemidirected, with a stereochemically active lone pair. In contrast, the structure of the PbBr2 adduct, although suffering from some disorder, shows a more typical, distorted arrangement of ligands; these results are discussed in terms of the tendency for soft, bulky ligands to promote symmetric, holodirected geometries. The ESI mass spectra of the adducts are reported, and yield [M−halide]⁺ ions.
Type
Journal Article
Type of thesis
Series
Citation
Henderson, W. & Hor, T.S.A. (2010). Synthesis and structural characterisation of the lead–platinum sulfido aggregates [Pt₂(μ-S)₂(PPh₃)₄PbX₂] (X = Br, I); promotion of rare tetrahedral geometry for lead(II). Inorganica Chimica Acta, 363(8), 1859-1863.
Date
2010-05-05
Publisher
Elsevier
Degree
Supervisors
Rights
This is an author’s accepted version of an article published in the journal: Inorganica Chimica Acta. © Elsevier Science B.V.