Department of Chemistry, Ege University, 35100 Bornova, Izmir, Turkey.
Dalton Trans. 2020 Dec 8;49(46):16903-16915. doi: 10.1039/d0dt02937h.
A series of RuII (1), RhIII (2), IrIII (3, 4), IrI (5) and PdII (6-9) complexes of the 'instant carbene' nitron were prepared and characterized by 1H- and 13C-NMR, FT-IR and elemental analysis. The molecular structures of complexes 1-4 and 6 were determined by X-ray diffraction studies. The catalytic activity of the complexes (1-9) was evaluated in alpha(α)-alkylation reactions of ketones with alcohol via the borrowing hydrogen strategy under mild conditions. These complexes were able to perform this catalytic transformation in a short time with low catalyst and base amounts under an air atmosphere. Also, the PdII-nitron complexes (6-9) were applied in the Suzuki-Miyaura C-C coupling reaction and these complexes successfully initiated this reaction in a short time (30 minutes) using the H2O/2-propanol (1.5 : 0.5) solvent system. The DFT calculations revealed that the Pd0/II/0 pathway was more preferable for the mechanism.
一系列 RuII（1）、RhIII（2）、IrIII（3、4）、IrI（5）和 PdII（6-9）配合物的“瞬时卡宾”硝酮被制备并通过 1H 和 13C-NMR、FT-IR 和元素分析进行了表征。配合物 1-4 和 6 的分子结构通过 X 射线衍射研究确定。这些配合物（1-9）在温和条件下通过借氢策略在酮与醇的 α（α）-烷基化反应中的催化活性进行了评估。这些配合物能够在空气气氛下，在短时间内以低催化剂和碱的用量进行这种催化转化。此外，PdII-硝酮配合物（6-9）也应用于 Suzuki-Miyaura C-C 偶联反应，这些配合物在短时间（30 分钟）内使用 H2O/2-丙醇（1.5:0.5）溶剂系统成功引发了该反应。DFT 计算表明，Pd0/II/0 途径对于该机制更为有利。
