Binuclear zinc(II) complex as an efficient catalyst for selective N-methylation reaction of amines with CO2 under mild reaction conditions

IF 2.8 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2026-02-01 Epub Date: 2025-11-22 DOI:10.1016/j.poly.2025.117902

Krishna Chandra Murmu , Debashis Saha , Juli Nanda Goswami , Urmila Saha , Bhriguram Das , Surajit Biswas , Ennio Zangrando , Malay Dolai

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Abstract

The capture and conversion of carbon dioxide from sustainable source has proven as a viable alternative in the production of key organic compounds. Here, the in-situ synthesis of a zinc metal complex, [Zn(II)₂(H₂L)(HL)](ClO₄)₃ (1), using 2-acetyl pyridine and succinic-hydrazide is addressed. The single crystal X-ray diffraction data of 1 revealed a dinuclear species with the two octahedral symmetry related zinc metal ions co-ordinated by a N₄O₂ donor set. Complex 1 acts as an efficient catalyst in the preparation of N-methylated products from amines through CO₂ fixation reaction. The involvement of cost effective polymethylhydrosiloxane (PMHS), a reducing agent obtained as a by-product from numerous reactions, makes this protocol more sustainable and environmentally friendly. A variety of N-methylated derivatives was produced from the correspondent aromatic amines with high yield and selectivity at 90 °C temperature under carbon dioxide at 1 atm pressure after 6–10 h of reaction. Even heterocyclic non aromatic amines furnished a very good percentage (96–98 %) of the desired N-methyl products via the same catalytic reaction in just 5 h of reaction time. The catalyst effectiveness of this catalysis process can be easily recognized by the high TON (2.2 × 10⁴–3.2 × 10⁴) and TOF values (2.2 × 10³–6.4 × 10³ h⁻¹) observed.

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双核锌（II）配合物在温和反应条件下作为胺与CO2选择性n -甲基化反应的高效催化剂

从可持续来源捕获和转化二氧化碳已被证明是生产关键有机化合物的可行替代方案。本文研究了以2-乙酰吡啶和琥珀酰肼为原料原位合成锌金属配合物[Zn(II)2(H2L)(HL)](ClO4)3(1)。单晶x射线衍射数据显示，1为双核物质，两个八面体对称相关的锌金属离子由N4O2供体配位。配合物1在胺通过CO2固定反应制备n -甲基化产物中起着高效催化剂的作用。聚甲基氢硅氧烷（PMHS）是一种从许多反应中获得的还原剂，具有成本效益，使该议定书更具可持续性和环境友好性。在90℃的温度下，在1atm的压力下，在二氧化碳条件下，经过6 ~ 10h的反应，得到了多种n -甲基化衍生物，收率高，选择性好。即使是杂环非芳香族胺，在同样的催化反应中，在5小时内也能得到很高比例（96 - 98%）的n -甲基产物。观察到的高TON值（2.2 × 104 ~ 3.2 × 104）和TOF值（2.2 × 103 ~ 6.4 × 103 h−1）可以很容易地识别出该催化过程的催化剂有效性。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.