{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T12:04:23Z","timestamp":1790337863001,"version":"4.1.0"},"reference-count":33,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T00:00:00Z","timestamp":1790208000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T00:00:00Z","timestamp":1790208000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2026,9,28]]},"abstract":"<jats:p>\n                    The catalytic cleavage of C\u2212H and C\u2212X (X\u2009=\u2009Cl, Br, I) bonds in alkanes and their halides over transition metals has drawn considerable attention due to the broad applicability in synthesizing commodity and fine chemicals. However, the dynamic reaction mechanisms of halomethanes on nanometals are still not fully understood. In this study, we report a comprehensive study into the gas\u2010phase reactivity of niobium clusters Nb\n                    <jats:italic>\n                      <jats:sub>n<\/jats:sub>\n                    <\/jats:italic>\n                    <jats:sup>\u2212<\/jats:sup>\n                    (\n                    <jats:italic>n<\/jats:italic>\n                    \u2009=\u20095\u201350) with haloalkanes CH\n                    <jats:sub>3<\/jats:sub>\n                    X (X\u2009=\u2009Cl, Br, I). These anionic clusters react vigorously with haloalkanes via an efficient demethylation pathway, yielding predominantly niobium\u2010halide products Nb\n                    <jats:sub>\n                      <jats:italic>n<\/jats:italic>\n                    <\/jats:sub>\n                    X\n                    <jats:sub>\n                      <jats:italic>m<\/jats:italic>\n                    <\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    , and the reactions of CH\n                    <jats:sub>3<\/jats:sub>\n                    I allow for both demethylation and dehydrogenation. Thermodynamic and kinetic analyses elucidate the reaction mechanisms and clarify how halogen substituents influence cluster\u2010mediated reactivity. This work provides a solid foundation for the rational design of niobium\u2010based catalysts constructed from superatom frameworks.\n                  <\/jats:p>","DOI":"10.1002\/cphc.70573","type":"journal-article","created":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T01:01:10Z","timestamp":1790298070000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["The Reactivity of Haloalkanes on Superatomic Niobium Clusters: Demethylation versus Dehydrogenation"],"prefix":"10.1002","volume":"27","author":[{"given":"Demiao","family":"Ma","sequence":"first","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences  Beijing P. R. China"},{"name":"School of Chemical Sciences University of Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xin","family":"Lei","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1968-6511","authenticated-orcid":false,"given":"Jianglu","family":"Yuan","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences  Beijing P. R. China"},{"name":"School of Chemical Sciences University of Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9746-3711","authenticated-orcid":false,"given":"Klavs","family":"Hansen","sequence":"additional","affiliation":[{"name":"Center for Joint Quantum Studies and Department of Physics School of Science Tianjin University  Tianjin P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5752-1996","authenticated-orcid":false,"given":"Zhixun","family":"Luo","sequence":"additional","affiliation":[{"name":"Beijing National Laboratory for Molecular Sciences (BNLMS) State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences  Beijing P. R. China"},{"name":"School of Chemical Sciences University of Chinese Academy of Sciences  Beijing P. R. 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