{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,23]],"date-time":"2025-11-23T23:16:15Z","timestamp":1763939775577,"version":"build-2065373602"},"reference-count":60,"publisher":"Wiley","issue":"14","license":[{"start":{"date-parts":[[2024,5,22]],"date-time":"2024-05-22T00:00:00Z","timestamp":1716336000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001843","name":"Science and Engineering Research Board","doi-asserted-by":"publisher","award":["CRG\/2021\/000759"],"award-info":[{"award-number":["CRG\/2021\/000759"]}],"id":[{"id":"10.13039\/501100001843","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["aces.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2024,7,15]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The Cu\u2212O\u2212Cu core exhibits methane\u2010to\u2010methanol conversion, mirroring the reactivity of the copper\u2013containing enzyme pMMO. Herein, we computationally examined the reactivity of a biomimetic Cu\u2212O\u2212Cu core towards methane\u2013to\u2013methanol conversion. The oxygen atom of the Cu\u2212O\u2212Cu core abstracts hydrogen present in the C\u2212H bond of methane. The spin density at the bridging oxygen helps to abstract hydrogen from the C\u2212H bond. We modulated the spin density of the bridging oxygen by substituting only a single copper atom of the Cu\u2212O\u2212Cu core by metals (M) such as Fe, Co, and Ag. These substitutions result in bimetallic [Cu\u2212O\u2212M]<jats:sup>2+<\/jats:sup> models. We observed that the energy barriers for the C\u2212H activation step and the subsequent rebound step vary with the metal M. [Cu\u2212O\u2212Ag]<jats:sup>2+<\/jats:sup> exhibits the highest reactivity for M2M conversion, while [Cu\u2212O\u2212Fe]<jats:sup>2+<\/jats:sup> displays the lowest reactivity. To understand the different reactivity of these models towards M2M conversion, we employed distortion\u2010interaction analysis, orbital analysis, spin density analysis, and quantum theory of atoms in molecules analysis. Orbital analysis reveals that all four adducts follow a hydrogen atom transfer mechanism for C\u2212H activation. Further, spin density analysis reveals that a higher spin density on the bridging oxygen leads to a lower C\u2212H activation barrier.<\/jats:p>","DOI":"10.1002\/asia.202400282","type":"journal-article","created":{"date-parts":[[2024,4,17]],"date-time":"2024-04-17T01:13:59Z","timestamp":1713316439000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Modelling on a Biomimetic [Cu\u2212O\u2212Cu]<sup>2+<\/sup>\u2013mediated Methane\u2013to\u2013Methanol Conversion Unveils the Site for Methane Activation"],"prefix":"10.1002","volume":"19","author":[{"given":"Sumangla","family":"Arora","sequence":"first","affiliation":[{"name":"Computational Catalysis Center Department of Chemistry Indian Institute of Technology Roorkee  Roorkee Uttarakhand 247667 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Puneet","family":"Gupta","sequence":"additional","affiliation":[{"name":"Computational Catalysis Center Department of Chemistry Indian Institute of Technology Roorkee  Roorkee Uttarakhand 247667 India"},{"name":"Center for Sustainable Energy Indian Institute of Technology Roorkee  Roorkee Uttarakhand 247667 India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,5,22]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4EE00604F"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1080\/10409230490475507"},{"key":"e_1_2_8_3_1","unstructured":"\u00a0"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi800598h"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic060739v"},{"key":"e_1_2_8_6_1","unstructured":"\u00a0"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic8003933"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja061604r"},{"key":"e_1_2_8_9_1","unstructured":"\u00a0"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202105167"},{"key":"e_1_2_8_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b00852"},{"key":"e_1_2_8_12_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0910461106"},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CP05435F"},{"key":"e_1_2_8_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CP05371J"},{"key":"e_1_2_8_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00344"},{"key":"e_1_2_8_16_1","unstructured":"\u00a0"},{"key":"e_1_2_8_17_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-023-01051-x"},{"key":"e_1_2_8_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c08834"},{"key":"e_1_2_8_19_1","unstructured":"\u00a0"},{"key":"e_1_2_8_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c02835"},{"key":"e_1_2_8_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b05320"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.7b00588"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CP04872J"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CP06696F"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201108363"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0911413106"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201003403"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201309505"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202101035"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201701486"},{"key":"e_1_2_8_31_1","unstructured":"\u00a0"},{"key":"e_1_2_8_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201805511"},{"key":"e_1_2_8_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ct400687b"},{"volume-title":"Oxford University Press.: Oxford","year":"1990","author":"Bader R. 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