Piano-stool dinuclear ruthenium (II) complexes of pyrazine-carboxylate/carboxamide ligands: Structural studies and catalytic transfer hydrogenation of ketones

IF 3.7 2区化学 Q2 CHEMISTRY, APPLIED

Applied Organometallic Chemistry Pub Date : 2023-09-26 DOI:10.1002/aoc.7269

Robert T. Kumah, Stephen O. Ojwach

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引用次数: 0

Abstract

Reactions of ligand pyrazine-2-carboxylic acid (HL1) with [Ru(η⁶-p-cymene)Cl₂]₂ precursor gave the dinuclear piano-stool ruthenium (II) complex [{Ru(η⁶-p-cymene)Cl₂}-μ-(L1)-{Ru(p-cymene)Cl}] (Ru1). Separately, reactions of N-(quinolin-8-yl) pyrazine-2-carboxamide (HL2), 5-methyl-N-(−(quinolin-8-yl) pyridine-2-carboxamide (HL3) and 5-chloro-N-(quinolin-8-yl) pyridine-2-carboxamide (HL4) with [Ru(η⁶-p-cymene)Cl₂]₂ dimer in the presence of KPF₆ afforded the cationic dinuclear complexes [{Ru(η⁶-p-cymene)Cl}₂-μ-(L2)][PF₆] (Ru2), [{Ru(η⁶-p-cymene)Cl}₂-μ-(L3)][Ru(L3)Cl₃] (Ru3) and [{Ru(η⁶-p-cymene)Cl}₂-μ-(L4)][PF₆] (Ru4). The Ru (II) complexes were analysed using FT-IR, ¹H, ¹³C{¹H}, ³¹P{¹H} (Ru2 and Ru4) and ¹⁹F (Ru2 and Ru4) NMR spectroscopic techniques, micro-analyses and mass spectrometry. Molecular structures of complexes Ru1 and Ru3 were confirmed to display piano-stool coordination nature using single-crystal X-ray crystallography analyses. All the complexes (Ru1–Ru4) mediated the transfer hydrogenation (TH) of a broad spectrum of ketones in isopropanol in the presence of a base and demonstrated high catalytic activities (TON of 24,000) at catalyst concentrations of 0.002 mol%. In general, the catalytic performance of these Ru (II) complexes depended on the identity of the ligands, coordination chemistry and ketone substrates.

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吡嗪羧酸盐/羧酰胺配体的钢琴凳双核钌（II）配合物：酮的结构研究和催化转移加氢反应

配体吡嗪-2-羧酸（HL1）与[Ru（η6-烯）Cl2]2前体反应，得到双核钢琴凳钌（II）配合物-{Ru（η-6-烯）Cl2}-。在KPF6存在下，N-（喹啉-8-基）吡嗪-2-甲酰胺（HL2）、5-甲基-N-（−（喹啉-8-基）吡啶-2-乙酰胺（HL3）和5-氯-N-（喹啉-8'-基）吡啶2-甲酰胺（HL4）与[Ru（η6-烯）Cl2]2二聚体的反应分别得到阳离子双核配合物-{Ru（η-6-烯）Cl}2-μ-（L2）][PF6]（Ru2），[｛Ru（η6-烯）Cl｝2-μ-（L3）][Ru（L3）Cl3]（Ru3）和[｛钌（η6-炔）Cl｝2μ-（L4）][PF6]（Ru4）。使用FT-IR、1H、13C{1H}、31P{1H}（Ru2和Ru4）和19F（Ru2与Ru4）NMR光谱技术、微观分析和质谱分析Ru（II）配合物。使用单晶X射线晶体学分析证实了配合物Ru1和Ru3的分子结构显示出钢琴凳配位性质。所有配合物（Ru1–Ru4）在碱存在下介导了异丙醇中广谱酮的转移氢化（TH），并在0.002的催化剂浓度下表现出高催化活性（TON为24000）摩尔%。通常，这些Ru（II）配合物的催化性能取决于配体的身份、配位化学和酮底物。

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来源期刊

Applied Organometallic Chemistry 化学-无机化学与核化学

CiteScore

7.80

自引率

10.30%

发文量

408

审稿时长

2.2 months

期刊介绍： All new compounds should be satisfactorily identified and proof of their structure given according to generally accepted standards. Structural reports, such as papers exclusively dealing with synthesis and characterization, analytical techniques, or X-ray diffraction studies of metal-organic or organometallic compounds will not be considered. The editors reserve the right to refuse without peer review any manuscript that does not comply with the aims and scope of the journal. Applied Organometallic Chemistry publishes Full Papers, Reviews, Mini Reviews and Communications of scientific research in all areas of organometallic and metal-organic chemistry involving main group metals, transition metals, lanthanides and actinides. All contributions should contain an explicit application of novel compounds, for instance in materials science, nano science, catalysis, chemical vapour deposition, metal-mediated organic synthesis, polymers, bio-organometallics, metallo-therapy, metallo-diagnostics and medicine. Reviews of books covering aspects of the fields of focus are also published.