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The combination of an electrophilic silylium carborate, such as [Me\n                    <jats:sub>3<\/jats:sub>\n                    Si(HCB\n                    <jats:sub>11<\/jats:sub>\n                    H\n                    <jats:sub>5<\/jats:sub>\n                    Br\n                    <jats:sub>6<\/jats:sub>\n                    )], and the nucleophilic phosphine\u2010coordinated palladium(0) complex (\n                    <jats:italic>o<\/jats:italic>\n                    \u2010Tol\n                    <jats:sub>3<\/jats:sub>\n                    P)\n                    <jats:sub>2<\/jats:sub>\n                    Pd, leads to the formation of the cationic silylpalladium adduct [(o\u2010Tol\n                    <jats:sub>3<\/jats:sub>\n                    P)\n                    <jats:sub>2<\/jats:sub>\n                    Pd\u2013SiMe\n                    <jats:sub>3<\/jats:sub>\n                    ]\n                    <jats:sup>+<\/jats:sup>\n                    , which catalyzes the silylation of allylbenzene derivatives using an allylsilane as the stoichiometric silicon electrophile. Mechanistic studies including DFT calculations support a mechanism involving regioselective stepwise ionic addition of the silylpalladium cation across the double bond followed by\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010hydride elimination to form a cationic palladium hydride. Exploiting the Br\u00f8nsted acidity of this intermediate facilitates the regeneration of the active silylpalladium complex by productive proton\u2010into\u2010silylium ion interconversion through deallylative protolysis (protodesilylation) of the allylsilane reagent, thereby maintaining the catalytic turnover. Hence, there is no need for an exogeneous base, whereas the conventional silyl\u2010Heck reaction requires the addition of (over)stoichiometric amounts of a base to trap the formed acid (HX) waste. Moreover, the established silyl\u2010Heck reaction relies on the oxidative addition of the silicon\u2013halogen bond of a halosilane electrophile as the critical step, while this synergistic process makes use of an allylsilane as the coupling partner, releasing propene as the sole by\u2010product.\n                  <\/jats:p>","DOI":"10.1002\/anie.5617321","type":"journal-article","created":{"date-parts":[[2026,9,12]],"date-time":"2026-09-12T17:18:00Z","timestamp":1789233480000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Synergistic Silylium\u2010Ion and Palladium Catalysis Enables Migratory Alkene Silylation With Allylsilanes by Formal C\u2013H\/C\u2013Si Metathesis"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-1549-7974","authenticated-orcid":false,"given":"Longhui","family":"Duan","sequence":"first","affiliation":[{"name":"Technische Universit\u00e4t Berlin Institut f\u00fcr Chemie Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6631-3681","authenticated-orcid":false,"given":"Zheng\u2010Wang","family":"Qu","sequence":"additional","affiliation":[{"name":"Rheinische Friedrich\u2010Wilhelms\u2010Universit\u00e4t Bonn Mulliken Center for Theoretical Chemistry, Clausius\u2010Institut f\u00fcr Physikalische und Theoretische Chemie Bonn Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5844-4371","authenticated-orcid":false,"given":"Stefan","family":"Grimme","sequence":"additional","affiliation":[{"name":"Rheinische Friedrich\u2010Wilhelms\u2010Universit\u00e4t Bonn Mulliken Center for Theoretical Chemistry, Clausius\u2010Institut f\u00fcr Physikalische und Theoretische Chemie Bonn Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6098-1996","authenticated-orcid":false,"given":"Elisabeth","family":"Irran","sequence":"additional","affiliation":[{"name":"Technische Universit\u00e4t Berlin Institut f\u00fcr Chemie Berlin Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3748-6609","authenticated-orcid":false,"given":"Hendrik F. 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