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Issue 36, 2018
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Amido Ca(II) complexes supported by Schiff base ligands for catalytic cross-dehydrogenative coupling of amines with silanes

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Abstract

A series of amido Ca complexes LCa[N(SiMe3)2](THF) (1–4) coordinated by Schiff base ligands L1–4 were synthesized via an amine elimination reaction between proligands L1–4H and a bisamido complex Ca[N(SiMe3)2]2(THF)2 in good yield. Unlike Ca[N(SiMe3)2]2(THF)2, the reactions of M[N(SiMe3)2]2(THF)2 (M = Yb, Sm) with proligands L1–4H do not lead to the formation of the target Ln(II) amido complexes. The reaction of Yb[N(SiMe3)2]2(THF)2 with L1H is accompanied by intramolecular C–H bond activation of a quinoline ring and results in the formation of complex 6 coordinated by a new trianionic [NNNNOO] ligand. The reactions of amido complexes 1 and 4 with PhSiH3 do not allow for preparing the related hydrides but afford homoleptic bis(phenolate) complexes 5 and 7 due to a ligand redistribution reaction. Amido complexes 1–4 were evaluated as precatalysts for cross-dehydrogenative coupling of silanes (PhSiH3, Ph(Me)SiH2, and Ph3SiH) and aliphatic, aromatic and cyclic amines (RNH2 and R2NH).

Graphical abstract: Amido Ca(ii) complexes supported by Schiff base ligands for catalytic cross-dehydrogenative coupling of amines with silanes

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Publication details

The article was received on 23 Mar 2018, accepted on 23 May 2018 and first published on 24 May 2018


Article type: Paper
DOI: 10.1039/C8DT01130C
Citation: Dalton Trans., 2018,47, 12570-12581

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    Amido Ca(II) complexes supported by Schiff base ligands for catalytic cross-dehydrogenative coupling of amines with silanes

    N. V. Forosenko, I. V. Basalov, A. V. Cherkasov, G. K. Fukin, E. S. Shubina and A. A. Trifonov, Dalton Trans., 2018, 47, 12570
    DOI: 10.1039/C8DT01130C

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