Issue 36, 2018

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

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

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
23 Mrz 2018
Accepted
23 Mai 2018
First published
24 Mai 2018

Dalton Trans., 2018,47, 12570-12581

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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