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用于CO间接加氢的贱金属催化剂。

Base Metal Catalyst for Indirect Hydrogenation of CO.

作者信息

Grover Jagrit, Maji Suman, Teja Chitrala, Al Thabaiti Shaeel A, Mostafa Mohamed Mokhtar M, Lahiri Goutam K, Maiti Debabrata

机构信息

Department of Chemistry, IIT Bombay, Powai, Mumbai 400076, India.

K. A. CARE Energy Research and Innovation Center, King Abdulaziz University, Jeddah 21589, Saudi Arabia, Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia.

出版信息

ACS Org Inorg Au. 2023 Jul 24;3(5):299-304. doi: 10.1021/acsorginorgau.3c00023. eCollection 2023 Oct 4.

DOI:10.1021/acsorginorgau.3c00023
PMID:37810409
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10557122/
Abstract

We herein report a novel Mn-SNS-based catalyst, which is capable of performing indirect hydrogenation of CO to methanol formylation. In this domain of CO hydrogenation, pincer ligands have shown a clear predominance. Our catalyst is based on the SNS-type tridentate ligand, which is quite stable and cheap as compared to the pincer type ligands. The catalyst can also be recycled effectively after the formylation reaction without any significant change in efficiency. Various amines including both primary and secondary amines worked well under the protocol to provide the desired formylated product in good yields. The formed formylated amines can also be reduced further at higher pressures of hydrogen. As a whole, we have developed a protocol that involves indirect CO hydrogenation to methanol that proceeds formylation of amines.

摘要

我们在此报告一种新型的基于Mn-SNS的催化剂,它能够将CO间接氢化为甲醇进行甲酰化反应。在CO加氢这个领域,钳形配体已显示出明显的优势。我们的催化剂基于SNS型三齿配体,与钳形配体相比,它相当稳定且便宜。该催化剂在甲酰化反应后也能有效回收,且效率没有任何显著变化。包括伯胺和仲胺在内的各种胺在该方案下都能很好地反应,以良好的产率提供所需的甲酰化产物。在更高的氢气压力下,生成的甲酰化胺也可以进一步还原。总体而言,我们开发了一种涉及将CO间接氢化为甲醇以进行胺的甲酰化反应的方案。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/5fa46136cdfe/gg3c00023_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/e09e97d8f372/gg3c00023_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/cb9e1b47b8af/gg3c00023_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/a6aa0646da4a/gg3c00023_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/76b7c9685dc0/gg3c00023_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/5fa46136cdfe/gg3c00023_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/e09e97d8f372/gg3c00023_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/cb9e1b47b8af/gg3c00023_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/a6aa0646da4a/gg3c00023_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/76b7c9685dc0/gg3c00023_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fd89/10557122/5fa46136cdfe/gg3c00023_0006.jpg

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本文引用的文献

1
Homogeneous Hydrogenation of CO and CO to Methanol: The Renaissance of Low-Temperature Catalysis in the Context of the Methanol Economy.一氧化碳和二氧化碳加氢制甲醇的均相氢化反应:甲醇经济背景下低温催化的复兴。
Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202207278. doi: 10.1002/anie.202207278. Epub 2022 Sep 14.
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Recent developments in first-row transition metal complex-catalyzed CO hydrogenation.第一过渡金属配合物催化 CO 加氢的最新进展。
Dalton Trans. 2022 May 31;51(21):8160-8168. doi: 10.1039/d2dt00663d.
3
State of the art and perspectives in heterogeneous catalysis of CO hydrogenation to methanol.
CO加氢制甲醇多相催化的研究现状与展望
Chem Soc Rev. 2020 Mar 7;49(5):1385-1413. doi: 10.1039/c9cs00614a. Epub 2020 Feb 18.
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Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis.二氧化碳经多相催化加氢制备甲醇的最新进展。
Chem Rev. 2020 Aug 12;120(15):7984-8034. doi: 10.1021/acs.chemrev.9b00723. Epub 2020 Feb 12.
5
Integrative CO Capture and Hydrogenation to Methanol with Reusable Catalyst and Amine: Toward a Carbon Neutral Methanol Economy.综合 CO 捕获与氢气化制备甲醇:可重复使用催化剂和胺的应用,迈向碳中和甲醇经济。
J Am Chem Soc. 2018 Feb 7;140(5):1580-1583. doi: 10.1021/jacs.7b12183. Epub 2018 Jan 24.
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Highly productive CO hydrogenation to methanol - a tandem catalytic approach via amide intermediates.通过酰胺中间体的串联催化方法实现高效的CO加氢制甲醇
Chem Commun (Camb). 2017 Aug 22;53(68):9502-9504. doi: 10.1039/c7cc04613h.
7
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO Hydrogenation Processes.多相催化CO加氢过程中绿色生产甲酸盐/甲酸、甲醇和二甲醚的挑战。
Chem Rev. 2017 Jul 26;117(14):9804-9838. doi: 10.1021/acs.chemrev.6b00816. Epub 2017 Jun 28.
8
Low-Temperature Hydrogenation of Carbon Dioxide to Methanol with a Homogeneous Cobalt Catalyst.低温二氧化碳加氢制甲醇用均相钴催化剂。
Angew Chem Int Ed Engl. 2017 Feb 6;56(7):1890-1893. doi: 10.1002/anie.201609077. Epub 2017 Jan 12.
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Tandem amine and ruthenium-catalyzed hydrogenation of CO2 to methanol.串联胺和钌催化二氧化碳加氢制甲醇。
J Am Chem Soc. 2015 Jan 28;137(3):1028-31. doi: 10.1021/ja511329m. Epub 2015 Jan 16.
10
Recycling of carbon dioxide to methanol and derived products - closing the loop.二氧化碳循环转化为甲醇和衍生产品——闭环循环。
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