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DALTON TRANSACTIONS · 2023 ·Vol. 52 ·期 35 ·12368-12377 · IF 4

Pyrazole–pyridine–pyrazole (NNN) ruthenium(II) complex catalyzed acceptorless dehydrogenation of alcohols to aldehydes

Yinyin Chen,Tianhua Cui,Hua Chen,Xue li Zheng,Haiyan Fu,Ruixiang Li

A new series of cationic ruthenium(II) complexes, [RuCl(PPh3)2(κ3-NNN-L1)]Cl (1), [RuH(PPh3)2(κ3-NNN-L2)]Cl (2), and [RuH(PPh3)2(κ3-NNN-L3)]Cl (3), bearing a 2,6-bis (1-R-5-methyl-pyrazol-3-yl) pyridine ligand (L1: R = H, L2: R = C6H4-p-CF3, L3: R = C6H4-p-OCH3), were synthesized and characterized with NMR, HRMS, and single-crystal X-ray diffraction. Their catalytic application was investigated in the acceptorless dehydrogenation (AD) of primary alcohols. Complex 1 outperformed 2 and 3 in terms of the selectivity towards the aldehydes, and provided the aldehydes with a yield of up to 99%, with good functional group tolerance under mild conditions. In addition, the only by-product of the reaction was dihydrogen, which can be collected as clean energy, and the reaction meets the requirements of environment-friendly chemistry. Complex 1 also proved to be a promising catalyst in the sequential AD/condensation reaction between the primary and secondary alcohols, affording α,β-unsaturated ketones in moderate to good selectivity.

研究领域: 无机化学 · 绿色化学
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MICROPOROUS AND MESOPOROUS MATERIALS · 2022 · IF 5.876

Insight into the liquid adsorption of tobacco specific nitrosamines on ZIF-8

Wen Bo Zhu,Ling Gao,Yu Kang Zhang,Qi Zhang,Ying Hong,Wei Jian Shen,Ying Wang,Jian Hua Zhu

Liquid adsorption of TSNA by ZIF-8 was studied in this paper for the first time, applying the deformable molecular sieve to adsorb and separate TSNA. ZIF-8 can adsorb the bulky NNK molecules whose size exceeds its pore size, whereas NaA and KA zeolites cannot though they have similar pore sizes. Moreover, ZIF-8 selectively adsorbed NNK in solution and reached adsorption equilibrium within 5 min. In contrast, NNN was hard to be adsorbed and easy to be eluted by water, which is useful for the separation of TSNA. The influence of solid-liquid (S/L) ratio and other factors on TSNA liquid adsorption was investigated in detail. When S/L was 0.2, ZIF-8 exerted the highest efficiency and the adsorption capacity per unit surface area reached 12–15 nmol. Through the comparison of adsorption of NNK, NNN and NPYR, it is found that the adsorption of TSNA by ZIF-8 depended on π-π electron interaction mainly, rather than geometric confinement effect. The liquid adsorption curve of NNK conforms to Langmuir isothermal adsorption model, and its saturated adsorption capacity Q m was estimated to be 4.34 mg g −1 , but actually it could reach 3.19 mg g −1 only. In addition, ZIF-8 had a mixing effect in liquid adsorption of TSNA: the presence of NNK promoted the adsorption of NNN slightly. ZIF-8 has the characteristics of fast adsorption and easy elution of TSNA in solution, which is beneficial for removal of TSNA to protect the environment and public health.

研究领域: 环境科学 · 公共卫生 · 材料科学
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JOURNAL OF ORGANIC CHEMISTRY · 2025 · IF 3.6

Ruthenium-Catalyzed Formal Hydroamination of Allyl Alcohols to γ-Amino Alcohols via a Borrowing Hydrogen Process

Mengxuan Bai,Xuetong Zhang,Shengxin Zhang,Caicai Zhang,Zhiqiang Hao,Jin Lin

γ-Amino alcohol is of great importance, as a broad number of bioactive and pharmaceutical alcohols contain this motif. Herein, a selective formal anti-Markovnikov hydroamination of allyl alcohols to access γ-amino alcohols has been achieved by using NNN-pincer Ru complexes. The electronic effect of the catalysts is critical for their catalytic performance. A wide substrate scope (65 examples) and up to 96% yields were achieved at low catalyst loadings via a borrowing hydrogen (BH) process in one pot. This protocol was easily extended to the hydroamination of both primary and secondary allyl alcohols and applications for the synthesis of drug derivatives.

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APPLIED ORGANOMETALLIC CHEMISTRY · 2020 ·Vol. 34 ·期 4 ·e5451 · IF 3.14

Ru(II)-PBTNNXN complex bearing functional 2-(pyridin-2-yl)benzo[d]thiazole ligand catalyzed α-alkylation of nitriles with alcohols

Shuang Huang,Xi Hong,Yong Sun,He-Zhen Cui,Quan Zhou,Yue-Jian Lin,Xiu-Feng Hou

Six tridentate NNN ligand precursors derived from 2-(pyridin-2-yl)benzo[d]thiazole(PBT) with different linkers, PBT NN X N (X = NH, NMe, O, S) ( 1a – 1f ), have been successfully prepared. The electronic properties of PBT NN X N ligands are well tunable by differing linkers between PBT skeleton and the pyridine ring, and/or by introducing electron-donating/withdrawing groups on the pyridine ring (R = OMe or F). The ligand precursors and representative complexes Ru ( PBT NN NH N )Cl 2 (PPh 3 ) ( 2a ), Ru ( PBT NN NMe N )Cl 2 (PPh 3 ) ( 2b ), and Ru ( PBT NN S N )Cl 2 (PPh 3 ) ( 2f ) have been characterized by NMR spectroscopy, high-resolution mass spectroscopy, and Fourier transform infrared (FT-IR). The molecular structures of 1f , 2a , and 2f have been determined by X-ray diffraction study. The results indicate that PBT NN NH N ligand in the complex presented coplanar with two five-membered chelating rings. It should be noted that 2a featuring a NH group exhibits superior performance compared to those with other linkers (such as NMe, O, or S). A variety of heterocyclic and aromatic nitriles with aromatic and aliphatic alcohols have been explored in α -alkylation for good to excellent yields. Based on kinetic experiments and mechanistic studies, a proposed mechanism was put forward. Ru-H species and benzaldehyde, which was oxidized from benzyl alcohol, were detected in the catalytic cycle.

研究领域: 无机化学 · 有机化学 · 催化 · 材料科学
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