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Issue 26, 2007
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Synthesis and theoretical studies on rare three-coordinate lead complexes

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Abstract

A series of β-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 β-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.

Graphical abstract: Synthesis and theoretical studies on rare three-coordinate lead complexes

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Article information


Submitted
27 Feb 2007
Accepted
20 Apr 2007
First published
17 May 2007

Dalton Trans., 2007, 2770-2778
Article type
Paper

Synthesis and theoretical studies on rare three-coordinate lead complexes

M. Chen, J. R. Fulton, P. B. Hitchcock, N. C. Johnstone, M. F. Lappert and A. V. Protchenko, Dalton Trans., 2007, 2770
DOI: 10.1039/B702994B

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