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Issue 36, 2014
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Lead and tin β-diketiminato amido/anilido complexes: competitive nucleophilic reactivity at the β-diketiminato γ-carbon

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Abstract

The β-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 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.

Graphical abstract: Lead and tin β-diketiminato amido/anilido complexes: competitive nucleophilic reactivity at the β-diketiminato γ-carbon

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Publication details

The article was received on 10 Jun 2014, accepted on 04 Aug 2014 and first published on 11 Aug 2014


Article type: Paper
DOI: 10.1039/C4DT01714E
Citation: Dalton Trans., 2014,43, 13803-13814
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    Lead and tin β-diketiminato amido/anilido complexes: competitive nucleophilic reactivity at the β-diketiminato γ-carbon

    L. A.-M. Harris, E. C. Y. Tam, M. P. Coles and J. R. Fulton, Dalton Trans., 2014, 43, 13803
    DOI: 10.1039/C4DT01714E

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