Synthesis and theoretical studies on rare three-coordinate lead complexes

Chen, Matthew, Fulton, J Robin, Hitchcock, Peter B, Johnstone, Nick C, Protchenko, Andrey V and Lappert, Michael F (2007) Synthesis and theoretical studies on rare three-coordinate lead complexes. Dalton Transactions, 26 (26). 2770 - 2778. ISSN 1477-9226

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Abstract

A series of ß-diketiminate lead halide complexes has been synthesised LPbCl (2), LPbBr (3) and LPbI (4) (L = {N(2,6-iPr2C6H3)C(Me)}2CH]), which includes a rare example of a three-coordinate lead iodide (4). The chloride and bromide complexes, 2 and 3, are relatively stable in both the solid and solution states, only slowly decomposing to elemental lead over the course of a month in solution, the lead iodide 4 appears to be less stable and decomposes after 3 d in the solid state at ambient temperatures. The lead chloride complex 2 was treated with KN(SiMe3)2 to yield an unusual terminal lead amide complex LPbN(SiMe3)2 (5). Unlike three-coordinate ß-diketiminate transition metal¿halide complexes, the ligands are present in a pyramidal arrangement around the lead centre, commonly attributed to the presence of a stereochemically active lone pair. We have investigated the influence of this lone pair on the geometry of the metal halide complexes 2¿4, as well as the isostructural germanium and tin complexes (6 and 7, respectively) using DFT calculations. The lone pair in the lead complexes is significantly more diffuse than in the tin and germanium analogues and only a small amount of hybridisation between the 6s and 6p orbitals is observed.

Item Type: Article
Additional Information: This is a comprehensive study into the structural stability of 3-coordinate lead halide complexes, including a theoretical investigation into the influence of the lone pair on the structure of the complexes. JRF supervised the work and is corresponding author
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Robin Fulton
Date Deposited: 06 Feb 2012 19:55
Last Modified: 26 Mar 2012 09:49
URI: http://srodev.sussex.ac.uk/id/eprint/23042
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