Department of Chemistry, University of Delhi, Delhi 110007, India.
Inorg Chem. 2021 Feb 1;60(3):2009-2022. doi: 10.1021/acs.inorgchem.0c03505. Epub 2021 Jan 18.
We present synthesis and characterization of two half-sandwich Ru(II) complexes supported with amide-phosphine based ligands. These complexes presented a pyridine-2,6-dicarboxamide based pincer cavity, decorated with hydrogen bonds, that participated in the binding of nitro-substrates closer to the Ru(II) centers, which is further supported with binding and docking studies. These ruthenium complexes functioned as the noteworthy catalysts for the borohydride mediated reduction of assorted nitro-substrates. Mechanistic studies not only confirmed the intermediacy of [Ru-H] in the reduction but also asserted the involvement of several organic intermediates during the course of the catalysis. A similar Ru(II) complex that lacked pyridine-2,6-dicarboxamide based pincer cavity substantiated its unique role both in the substrate binding and the subsequent catalysis.
我们介绍了两种半夹心 Ru(II) 配合物的合成和表征，它们都以酰胺-膦基配体为支撑。这些配合物呈现出吡啶-2,6-二甲酰胺为基础的钳子空腔，由氢键修饰，参与了硝基底物更接近 Ru(II) 中心的结合，这进一步得到了结合和对接研究的支持。这些钌配合物作为硼氢化物介导的各种硝基底物还原的显著催化剂。机理研究不仅证实了还原过程中[Ru-H]的中间体的存在，还证明了在催化过程中涉及到几种有机中间体。一个缺乏吡啶-2,6-二甲酰胺为基础的钳子空腔的类似 Ru(II) 配合物证实了它在底物结合和随后的催化过程中独特的作用。
