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Dalton Trans ; 43(36): 13803-14, 2014 Sep 28.
Article in English | MEDLINE | ID: mdl-25109774

ABSTRACT

The ß-diketiminatolead(II)-amido and -anilido complexes, [(BDI)Pb(NRR')] (BDI = [{N(2,6-iPr2C6H3)C(Me)}2CH]; NRR' = NH(2,6-iPr2C6H3), 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 ß-diketiminato ligand to form a complex that is the net result of a nucleophilic attack by the γ-carbon atom of the ß-diketiminato ligand at the electrophilic carbon centre of phenylisocyanate. As this reactivity contrasts with that of ß-diketiminatolead(II) alkoxo complexes as well as ß-diketiminatotin(II) alkoxo complexes, we examined the reactivity between phenylisocyanate and the isostructural ß-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.

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