G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603137, 49 Tropinina str., Nizhny Novgorod, GSP-445, Russia.
Dalton Trans. 2018 Sep 18;47(36):12570-12581. doi: 10.1039/c8dt01130c.
A series of amido Ca complexes LCaN(SiMe3)2 (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).
通过前体 L1-4H 与双酰胺配合物 Ca[N(SiMe3)2]2(THF)2 之间的胺消除反应，合成了一系列由席夫碱配体 L1-4 配位的酰胺 Ca 配合物 LCaN(SiMe3)2（1-4），产率良好。与 Ca[N(SiMe3)2]2(THF)2 不同，M[N(SiMe3)2]2(THF)2（M=Yb、Sm）与前体 L1-4H 的反应不会导致目标 Ln(ii)酰胺配合物的形成。Yb[N(SiMe3)2]2(THF)2 与 L1H 的反应伴随着喹啉环的分子内 C-H 键活化，导致由新的三阴离子[NNNNOO]配体配位的配合物 6 的形成。酰胺配合物 1 和 4 与 PhSiH3 的反应不能制备相关的氢化物，但由于配体重新分布反应，得到了均配的双（酚盐）配合物 5 和 7。酰胺配合物 1-4 被评估为硅烷（PhSiH3、Ph(Me)SiH2 和 Ph3SiH）和脂肪族、芳香族和环状胺（RNH2 和 R2NH）的交叉脱氢偶联的前催化剂。
