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钌(II)羰基配合物,带有基于喹啉的 NNO 三齿配体,用作醛一锅法转化为酰胺和邻烯丙基化酚的催化剂。

Ruthenium(II) carbonyl complexes bearing quinoline-based NNO tridentate ligands as catalyst for one-pot conversion of aldehydes to amides and o-allylation of phenols.

机构信息

Department of Chemistry, Periyar University, Salem 636 011, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2013 Dec;116:501-8. doi: 10.1016/j.saa.2013.07.114. Epub 2013 Aug 9.

Abstract

Six new octahedral ruthenium(II) carbonyl complexes having the general molecular formula [RuCl(CO)(B)L(1-2)] (B = PPh3, AsPh3 or py; L(1-2) = quinoline based NNO ligand) were synthesized. The quinoline based ligands behave as monoanionic tridentate donor and coordinated to ruthenium via ketoenolate oxygen, azomethine nitrogen and quinoline nitrogen. The composition of the complexes has been established by elemental analysis and spectral methods (FT-IR, electronic, (1)H NMR, (13)C NMR, (31)P NMR and ESI-Mass). The complexes were used as efficient catalysts for one-pot conversion of various aldehydes to their corresponding primary amides in presence of NH2OH · HCl and NaHCO3. The effect of catalyst loading and reaction temperature on catalytic activity of the ruthenium(II) carbonyl complexes were also investigated. The synthesized complexes also possess good catalytic activity for the o-allylation of phenols in the presence of K2CO3 under mild conditions. The complexes afforded branched allyl aryl ethers according to a regioselective reaction.

摘要

合成了六个具有通式[RuCl(CO)(B)L(1-2)]的新型八面体钌(II)羰基配合物(B = PPh3、AsPh3 或 py;L(1-2) = 基于喹啉的 NNO 配体)。基于喹啉的配体表现为单价阴离子三齿供体,并通过酮烯醇氧、亚氨基氮和喹啉氮与钌配位。配合物的组成通过元素分析和光谱方法(FT-IR、电子、(1)H NMR、(13)C NMR、(31)P NMR 和 ESI-Mass)确定。在 NH2OH·HCl 和 NaHCO3 的存在下,这些配合物可用作将各种醛一锅法转化为相应伯酰胺的有效催化剂。还研究了催化剂负载量和反应温度对钌(II)羰基配合物催化活性的影响。在温和条件下,在 K2CO3 的存在下,这些合成的配合物也对苯酚的 o-烯丙基化具有良好的催化活性。根据区域选择性反应,配合物提供支链烯丙基芳基醚。

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