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在酰胺的分子间α-芳基化反应中,双核钯(II)NHC/PCy配合物比其单核对应物具有更好的催化效果。

Superior Catalytic Outcomes of Dinuclear Palladium(II) NHC/PCy Complex Over Its Mononuclear Counterpart in Intermolecular α-Arylation of Amide.

作者信息

Goswami Sneha, Sarker Kaustav, Bandyopadhyay Uchchhal, Mondal Debarati, Halder Ankita, Maity Ramananda

机构信息

Department of Chemistry, University of Calcutta, 92-APC Road, Kolkata, 700009, India.

出版信息

Chem Asian J. 2025 Jul;20(14):e202500507. doi: 10.1002/asia.202500507. Epub 2025 May 6.

Abstract

Cooperation between metal centers appeared to be beneficial in many catalytic transformations when the metal centers are placed on a properly designed poly-NHC ligand platform. However, examples of such NHC ligand platforms are limited. Dinuclear palladium(II) complexes comprising bis-imidazolylidene along with pyridine or tricyclohexylphosphine (PCy) as ancillary ligands were synthesized and characterized by using standard spectroscopic techniques. The dinuclear bis-NHC complex with PCy as an ancillary ligand appeared to be a highly active precatalyst for the intermolecular α-arylation of 1-methyl-2-oxindole and this complex appeared to be beneficial over its corresponding mononuclear complex in terms of catalytic outcomes which is possibly due to the cooperative action between two palladium(II) centers during catalysis. The DLS measurements were performed which indicates the homogeneous nature of the aforementioned catalysis.

摘要

当金属中心置于精心设计的聚氮杂环卡宾(poly-NHC)配体平台上时,金属中心之间的合作在许多催化转化中似乎是有益的。然而,这种氮杂环卡宾配体平台的例子有限。合成了包含双咪唑啉亚基以及吡啶或三环己基膦(PCy)作为辅助配体的双核钯(II)配合物,并使用标准光谱技术对其进行了表征。以PCy作为辅助配体的双核双氮杂环卡宾配合物似乎是1-甲基-2-氧代吲哚分子间α-芳基化的高活性预催化剂,并且就催化结果而言,该配合物似乎比其相应的单核配合物更具优势,这可能是由于两个钯(II)中心在催化过程中的协同作用。进行了动态光散射(DLS)测量,结果表明上述催化具有均相性质。

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