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This depends on the low\u2010temperature formation of the methoxy intermediate required for methylation. Here, we establish a route for methoxy formation in which formic acid (FA) hydrogenates via a metastable monodentate formate intermediate. With the GaZrO\n                    <jats:italic>\n                      <jats:sub>x<\/jats:sub>\n                    <\/jats:italic>\n                    \u2013ZSM\u20105 catalyst, Ga\u2013H bonds act as a \u201cplaceholder\u201d, enabling FA adsorption as a monodentate formate rather than a stable bridged formate. At 300\u00a0\u00b0C and 3.0\u00a0MPa, toluene conversion reaches 13.9% with 77.6% xylene selectivity, outperforming established routes. Kinetic isotope effect experiments revealed that Ga\u2010based catalysts show a secondary isotope effect, whereas non\u2010Ga catalysts exhibit an inverse isotope effect. Density functional theory calculations indicated that the monodentate formate was more susceptible to hydrogenation which then facilitated methylation. This work provides a competitive route for xylene production from toluene under mild conditions using sustainable FA and H\n                    <jats:sub>2<\/jats:sub>\n                    .\n                  <\/jats:p>","DOI":"10.1002\/anie.202524831","type":"journal-article","created":{"date-parts":[[2026,1,14]],"date-time":"2026-01-14T07:14:20Z","timestamp":1768374860000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Monodentate Formate\u2010Mediated Toluene Methylation to Xylene at Low Temperature Using Formic Acid and Hydrogen"],"prefix":"10.1002","volume":"65","author":[{"given":"Jiachang","family":"Zuo","sequence":"first","affiliation":[{"name":"State Key Laboratory of Physical Chemistry of Solid Surfaces National Engineering Laboratory for Green Chemical Productions of Alcohols\u2010Ethers\u2010Esters College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"},{"name":"Fujian Key Laboratory of Pollution Control and Resource Reuse College of Environmental and Resource Sciences Fujian Normal University  Fuzhou 350007 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chong","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou 350000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bilyu","family":"Hong","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Physical Chemistry of Solid Surfaces National Engineering Laboratory for Green Chemical Productions of Alcohols\u2010Ethers\u2010Esters College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qiongjin","family":"Jiang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Physical Chemistry of 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