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Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol

Synthetic homogeneous system known to date performing methane to methanol conversion using O(2) as terminal oxidant is unique and based on copper complex with piperazine-based ligand (Cu(3)L in Fig. 1) in a medium of acetonitrile. Prior work have shown that in order to achieve catalytic turnover, hy...

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Autores principales: Moharreri, Ehsan, Jafari, Tahereh, Rathnayake, Dinithi, Khanna, Harshul, Kuo, Chung-Hao, Suib, Steven L., Nandi, Partha
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8478979/
https://www.ncbi.nlm.nih.gov/pubmed/34584179
http://dx.doi.org/10.1038/s41598-021-98721-2
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author Moharreri, Ehsan
Jafari, Tahereh
Rathnayake, Dinithi
Khanna, Harshul
Kuo, Chung-Hao
Suib, Steven L.
Nandi, Partha
author_facet Moharreri, Ehsan
Jafari, Tahereh
Rathnayake, Dinithi
Khanna, Harshul
Kuo, Chung-Hao
Suib, Steven L.
Nandi, Partha
author_sort Moharreri, Ehsan
collection PubMed
description Synthetic homogeneous system known to date performing methane to methanol conversion using O(2) as terminal oxidant is unique and based on copper complex with piperazine-based ligand (Cu(3)L in Fig. 1) in a medium of acetonitrile. Prior work have shown that in order to achieve catalytic turnover, hydrogen peroxide is needed to regenerate the active site. We show in this paper that reaction solvent based on organic nitrile decompose concurrently with methane activation and that in the absence of either acetonitrile, Cu complex or hydrogen peroxide, the catalytic turnover does not happen. We show in this manuscript that the direct methane oxidation to methanol might have been mediated by catalytic Radziszewski oxidation between acetonitrile and H(2)O(2). Additionally we have discovered that in the absence of methane, peroxide mediated acetonitrile decomposition also makes methanol via a background reaction which was hitherto unknown.
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spelling pubmed-84789792021-09-30 Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol Moharreri, Ehsan Jafari, Tahereh Rathnayake, Dinithi Khanna, Harshul Kuo, Chung-Hao Suib, Steven L. Nandi, Partha Sci Rep Article Synthetic homogeneous system known to date performing methane to methanol conversion using O(2) as terminal oxidant is unique and based on copper complex with piperazine-based ligand (Cu(3)L in Fig. 1) in a medium of acetonitrile. Prior work have shown that in order to achieve catalytic turnover, hydrogen peroxide is needed to regenerate the active site. We show in this paper that reaction solvent based on organic nitrile decompose concurrently with methane activation and that in the absence of either acetonitrile, Cu complex or hydrogen peroxide, the catalytic turnover does not happen. We show in this manuscript that the direct methane oxidation to methanol might have been mediated by catalytic Radziszewski oxidation between acetonitrile and H(2)O(2). Additionally we have discovered that in the absence of methane, peroxide mediated acetonitrile decomposition also makes methanol via a background reaction which was hitherto unknown. Nature Publishing Group UK 2021-09-28 /pmc/articles/PMC8478979/ /pubmed/34584179 http://dx.doi.org/10.1038/s41598-021-98721-2 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Moharreri, Ehsan
Jafari, Tahereh
Rathnayake, Dinithi
Khanna, Harshul
Kuo, Chung-Hao
Suib, Steven L.
Nandi, Partha
Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol
title Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol
title_full Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol
title_fullStr Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol
title_full_unstemmed Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol
title_short Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol
title_sort role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8478979/
https://www.ncbi.nlm.nih.gov/pubmed/34584179
http://dx.doi.org/10.1038/s41598-021-98721-2
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