Mechanistic insights into aerobic oxidative cleavage of glycol catalyzed by an Anderson-type polyoxometalate [IMo6O24]5
A computational investigation of the aerobic oxidative C–C bond cleavage reaction of glycol catalyzed by an Anderson-type heteropolyanion HPA [IMo 6 O 24 ] 5− in the presence of acetonitrile as solvent has been performed at the WB97XD/6-31G(d,p)/lanl2dz level. Two reaction pathways have been identif...
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| Veröffentlicht in: | Journal of molecular modeling 2023-02, Vol.29 (2), p.57-57, Article 57 |
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| creator | Almi, Meriem Zhou, Meijuan Saal, Amar Springborg, Michael |
| description | A computational investigation of the aerobic oxidative C–C bond cleavage reaction of glycol catalyzed by an Anderson-type heteropolyanion HPA [IMo
6
O
24
]
5−
in the presence of acetonitrile as solvent has been performed at the WB97XD/6-31G(d,p)/lanl2dz level. Two reaction pathways have been identified. The catalytic cycle of each pathway consists of three steps: oxidation cleavage of a glycol molecule by the HPA, oxidation of the HPA by one dioxygen molecule, and, finally, oxidation of a second glycol and regeneration of the catalyst. These reaction pathways have been thoroughly investigated in terms of energetic, natural bond orbital (NBO), natural charges, and geometrical parameters. It is found that (i) even though the top oxygen atoms of the Anderson heteropolyanion are not the most negatively charged ones, they are more likely to react with the diol hydroxyl groups, (ii) a direct relationship between the presence of the iodine ion I(VII) and the studied oxidation reaction could not be identified, and (iii) in terms of energy, the transfer of the two hydrogen atoms is the most energetic step.
Graphical abstract |
| doi_str_mv | 10.1007/s00894-023-05458-y |
| format | Article |
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6
O
24
]
5−
in the presence of acetonitrile as solvent has been performed at the WB97XD/6-31G(d,p)/lanl2dz level. Two reaction pathways have been identified. The catalytic cycle of each pathway consists of three steps: oxidation cleavage of a glycol molecule by the HPA, oxidation of the HPA by one dioxygen molecule, and, finally, oxidation of a second glycol and regeneration of the catalyst. These reaction pathways have been thoroughly investigated in terms of energetic, natural bond orbital (NBO), natural charges, and geometrical parameters. It is found that (i) even though the top oxygen atoms of the Anderson heteropolyanion are not the most negatively charged ones, they are more likely to react with the diol hydroxyl groups, (ii) a direct relationship between the presence of the iodine ion I(VII) and the studied oxidation reaction could not be identified, and (iii) in terms of energy, the transfer of the two hydrogen atoms is the most energetic step.
Graphical abstract</description><identifier>ISSN: 1610-2940</identifier><identifier>EISSN: 0948-5023</identifier><identifier>DOI: 10.1007/s00894-023-05458-y</identifier><identifier>PMID: 36710274</identifier><language>eng</language><publisher>Berlin/Heidelberg: Springer Berlin Heidelberg</publisher><subject>Acetonitrile ; catalysts ; Characterization and Evaluation of Materials ; Chemistry ; Chemistry and Materials Science ; Cleavage ; cleavage (chemistry) ; Computer Appl. in Life Sciences ; Computer Applications in Chemistry ; Covalent bonds ; energy ; Heteropoly anions ; hydrogen ; Hydrogen atoms ; Hydroxyl groups ; Iodine ; Molecular Medicine ; Original Paper ; Oxidation ; oxygen ; Oxygen atoms ; Polyoxometallates ; solvents ; Theoretical and Computational Chemistry</subject><ispartof>Journal of molecular modeling, 2023-02, Vol.29 (2), p.57-57, Article 57</ispartof><rights>The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023. Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.</rights><rights>2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c338t-c5a4ac9820c838195be5db9ef1156eb553788f5a87e86148adcf32a28fe715013</citedby><cites>FETCH-LOGICAL-c338t-c5a4ac9820c838195be5db9ef1156eb553788f5a87e86148adcf32a28fe715013</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1007/s00894-023-05458-y$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1007/s00894-023-05458-y$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,776,780,27901,27902,41464,42533,51294</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/36710274$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Almi, Meriem</creatorcontrib><creatorcontrib>Zhou, Meijuan</creatorcontrib><creatorcontrib>Saal, Amar</creatorcontrib><creatorcontrib>Springborg, Michael</creatorcontrib><title>Mechanistic insights into aerobic oxidative cleavage of glycol catalyzed by an Anderson-type polyoxometalate [IMo6O24]5</title><title>Journal of molecular modeling</title><addtitle>J Mol Model</addtitle><addtitle>J Mol Model</addtitle><description>A computational investigation of the aerobic oxidative C–C bond cleavage reaction of glycol catalyzed by an Anderson-type heteropolyanion HPA [IMo
6
O
24
]
5−
in the presence of acetonitrile as solvent has been performed at the WB97XD/6-31G(d,p)/lanl2dz level. Two reaction pathways have been identified. The catalytic cycle of each pathway consists of three steps: oxidation cleavage of a glycol molecule by the HPA, oxidation of the HPA by one dioxygen molecule, and, finally, oxidation of a second glycol and regeneration of the catalyst. These reaction pathways have been thoroughly investigated in terms of energetic, natural bond orbital (NBO), natural charges, and geometrical parameters. It is found that (i) even though the top oxygen atoms of the Anderson heteropolyanion are not the most negatively charged ones, they are more likely to react with the diol hydroxyl groups, (ii) a direct relationship between the presence of the iodine ion I(VII) and the studied oxidation reaction could not be identified, and (iii) in terms of energy, the transfer of the two hydrogen atoms is the most energetic step.
Graphical abstract</description><subject>Acetonitrile</subject><subject>catalysts</subject><subject>Characterization and Evaluation of Materials</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Cleavage</subject><subject>cleavage (chemistry)</subject><subject>Computer Appl. in Life Sciences</subject><subject>Computer Applications in Chemistry</subject><subject>Covalent bonds</subject><subject>energy</subject><subject>Heteropoly anions</subject><subject>hydrogen</subject><subject>Hydrogen atoms</subject><subject>Hydroxyl groups</subject><subject>Iodine</subject><subject>Molecular Medicine</subject><subject>Original Paper</subject><subject>Oxidation</subject><subject>oxygen</subject><subject>Oxygen atoms</subject><subject>Polyoxometallates</subject><subject>solvents</subject><subject>Theoretical and Computational Chemistry</subject><issn>1610-2940</issn><issn>0948-5023</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNqFkU1v1DAQhi0EoqvSP8ABWeLCxTD-do5VBaVSq17gVFWW40y2qbLxEntL01-PyxaQOMDJ1swzr-V5CHnN4T0HsB8ygGsUAyEZaKUdW56RFTTKMV1rz8mKGw5MNAoOyFHOtwDAhTZaiJfkQBrLQVi1It8vMN6EachliHSY8rC-KbleSqIB59TWarofulCGO6RxxHAX1khTT9fjEtNIYyhhXB6wo-1Cw0SPpw7nnCZWli3SbRqXdJ82WKFQkF6dXSRzKdS1fkVe9GHMePR0HpKvnz5-OfnMzi9Pz06Oz1mU0hUWdVAhNk5AdNLxRreou7bBnnNtsNVaWud6HZxFZ7hyoYu9FEG4Hi3XwOUhebfP3c7p2w5z8ZshRxzHMGHaZS-cs0Zy4Zr_o7YuzWkrbUXf_oXept081Y88UmC5aYyqlNhTcU45z9j77Txswrx4Dv5Rot9L9FWY_ynRL3XozVP0rt1g93vkl7IKyD2Qa2ta4_zn7X_E_gC8xKe2</recordid><startdate>20230201</startdate><enddate>20230201</enddate><creator>Almi, Meriem</creator><creator>Zhou, Meijuan</creator><creator>Saal, Amar</creator><creator>Springborg, Michael</creator><general>Springer Berlin Heidelberg</general><general>Springer Nature B.V</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7S9</scope><scope>L.6</scope></search><sort><creationdate>20230201</creationdate><title>Mechanistic insights into aerobic oxidative cleavage of glycol catalyzed by an Anderson-type polyoxometalate [IMo6O24]5</title><author>Almi, Meriem ; Zhou, Meijuan ; Saal, Amar ; Springborg, Michael</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c338t-c5a4ac9820c838195be5db9ef1156eb553788f5a87e86148adcf32a28fe715013</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Acetonitrile</topic><topic>catalysts</topic><topic>Characterization and Evaluation of Materials</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Cleavage</topic><topic>cleavage (chemistry)</topic><topic>Computer Appl. in Life Sciences</topic><topic>Computer Applications in Chemistry</topic><topic>Covalent bonds</topic><topic>energy</topic><topic>Heteropoly anions</topic><topic>hydrogen</topic><topic>Hydrogen atoms</topic><topic>Hydroxyl groups</topic><topic>Iodine</topic><topic>Molecular Medicine</topic><topic>Original Paper</topic><topic>Oxidation</topic><topic>oxygen</topic><topic>Oxygen atoms</topic><topic>Polyoxometallates</topic><topic>solvents</topic><topic>Theoretical and Computational Chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Almi, Meriem</creatorcontrib><creatorcontrib>Zhou, Meijuan</creatorcontrib><creatorcontrib>Saal, Amar</creatorcontrib><creatorcontrib>Springborg, Michael</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><jtitle>Journal of molecular modeling</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Almi, Meriem</au><au>Zhou, Meijuan</au><au>Saal, Amar</au><au>Springborg, Michael</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanistic insights into aerobic oxidative cleavage of glycol catalyzed by an Anderson-type polyoxometalate [IMo6O24]5</atitle><jtitle>Journal of molecular modeling</jtitle><stitle>J Mol Model</stitle><addtitle>J Mol Model</addtitle><date>2023-02-01</date><risdate>2023</risdate><volume>29</volume><issue>2</issue><spage>57</spage><epage>57</epage><pages>57-57</pages><artnum>57</artnum><issn>1610-2940</issn><eissn>0948-5023</eissn><abstract>A computational investigation of the aerobic oxidative C–C bond cleavage reaction of glycol catalyzed by an Anderson-type heteropolyanion HPA [IMo
6
O
24
]
5−
in the presence of acetonitrile as solvent has been performed at the WB97XD/6-31G(d,p)/lanl2dz level. Two reaction pathways have been identified. The catalytic cycle of each pathway consists of three steps: oxidation cleavage of a glycol molecule by the HPA, oxidation of the HPA by one dioxygen molecule, and, finally, oxidation of a second glycol and regeneration of the catalyst. These reaction pathways have been thoroughly investigated in terms of energetic, natural bond orbital (NBO), natural charges, and geometrical parameters. It is found that (i) even though the top oxygen atoms of the Anderson heteropolyanion are not the most negatively charged ones, they are more likely to react with the diol hydroxyl groups, (ii) a direct relationship between the presence of the iodine ion I(VII) and the studied oxidation reaction could not be identified, and (iii) in terms of energy, the transfer of the two hydrogen atoms is the most energetic step.
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| subjects | Acetonitrile catalysts Characterization and Evaluation of Materials Chemistry Chemistry and Materials Science Cleavage cleavage (chemistry) Computer Appl. in Life Sciences Computer Applications in Chemistry Covalent bonds energy Heteropoly anions hydrogen Hydrogen atoms Hydroxyl groups Iodine Molecular Medicine Original Paper Oxidation oxygen Oxygen atoms Polyoxometallates solvents Theoretical and Computational Chemistry |
| title | Mechanistic insights into aerobic oxidative cleavage of glycol catalyzed by an Anderson-type polyoxometalate [IMo6O24]5 |
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