946532-53-2Relevant academic research and scientific papers
Synthesis and theoretical studies on rare three-coordinate lead complexes
Chen, Matthew,Fulton, J. Robin,Hitchcock, Peter B.,Johnstone, Nick C.,Lappert, Michael F.,Protchenko, Andrey V.
, p. 2770 - 2778 (2007)
A series of β-diketiminate lead halide complexes has been synthesised LPbCl (2), LPbBr (3) and LPbI (4) (L = {N(2,6-iPr2C 6H3)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. The Royal Society of Chemistry 2007.
Lead and tin β-diketiminato amido/anilido complexes: Competitive nucleophilic reactivity at the β-diketiminato γ-carbon
Harris, Lisa A.-M.,Tam, Eric C.Y.,Coles, Martyn P.,Fulton, J. Robin
, p. 13803 - 13814 (2014)
The β-diketiminatolead(ii)-amido and -anilido complexes, [(BDI)Pb(NRR′)] (BDI = [{N(2,6-iPr2C6H 3)C(Me)}2CH]; NRR′ = NH(2,6-iPr2C 6H3), N(iPr)2), react at the amido/anilido nitrogen atom with simple saturated electrophiles such as methyltriflate. Addition of unsaturated electrophiles to these complexes either results in the formation of a complex mixture of products, or in the case of phenylisocyanate, reaction at the γ-carbon of the β-diketiminato ligand to form a complex that is the net result of a nucleophilic attack by the γ-carbon atom of the β-diketiminato ligand at the electrophilic carbon centre of phenylisocyanate. As this reactivity contrasts with that of β- diketiminatolead(II) alkoxo complexes as well as β-diketiminatotin(II) alkoxo complexes, we examined the reactivity between phenylisocyanate and the isostructural β-diketiminatotin(II)-amido and -anilido complexes. Reactivity at the γ-carbon was also observed in these systems. Density functional calculations were performed to help understand the differences in reactivity. the Partner Organisations 2014.
