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The optimal catalytic system operates under mild conditions and exhibits an unprecedented \u201cterminal\u2010only\u201d selectivity. It quantitatively discriminates between terminal and internal or multi\u2010substituted double bonds, which has been a long\u2010standing challenge in oxo synthesis. Traditional systems often trigger the isomerization of internal olefins, but our catalyst leaves them untouched, even within complex industrial feedstocks. Comprehensive mechanistic investigations, including in situ IR spectroscopy and high\u2010pressure VT NMR spectroscopy, identify the tetranuclear ruthenium\u2010hydride cluster [DBUH]\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    [H\n                    <jats:sub>2<\/jats:sub>\n                    Ru\n                    <jats:sub>4<\/jats:sub>\n                    (CO)\n                    <jats:sub>12<\/jats:sub>\n                    ]\n                    <jats:sup>2\u2212<\/jats:sup>\n                    as the pivotal active species. Isolating this cluster and successfully reapplying it confirms its role as the catalytic resting state. Combining low\u2010cost, air\u2010stable components with exceptional chemo\u2010 and regioselectivity provides this system with a robust, economically superior alternative to precious rhodium\u2010phosphine catalysts for academic synthesis and large\u2010scale industrial applications\n.\n                  <\/jats:p>","DOI":"10.1002\/anie.3316419","type":"journal-article","created":{"date-parts":[[2026,7,23]],"date-time":"2026-07-23T19:31:06Z","timestamp":1784835066000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Exclusive Hydroformylation of Terminal Olefins: A Phosphorus\u2010Free Ruthenium System for the Selective Functionalization of Complex Mixtures"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1039-7593","authenticated-orcid":false,"given":"Mohamed Niyaz","family":"Vellala Syed Ali","sequence":"first","affiliation":[{"name":"Department of Applied Homogeneous Catalysis Leibniz\u2010Institut f\u00fcr Katalyse e. V. Albert\u2010Einstein\u2010Stra\u00dfe 29a  Rostock Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3591-0787","authenticated-orcid":false,"given":"Ida","family":"Ziccarelli","sequence":"additional","affiliation":[{"name":"Laboratory of Industrial and Synthetic Organic Chemistry (LISOC) Department of Chemistry and Chemical Technologies University of Calabria  Arcavacata di Rende Cosenza Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dilver Pe\u00f1a","family":"Fuentes","sequence":"additional","affiliation":[{"name":"Department of Applied Homogeneous Catalysis Leibniz\u2010Institut f\u00fcr Katalyse e. V. Albert\u2010Einstein\u2010Stra\u00dfe 29a  Rostock Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Christoph","family":"Kubis","sequence":"additional","affiliation":[{"name":"Department of Applied Homogeneous Catalysis Leibniz\u2010Institut f\u00fcr Katalyse e. V. Albert\u2010Einstein\u2010Stra\u00dfe 29a  Rostock Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Robert","family":"Franke","sequence":"additional","affiliation":[{"name":"Evonik Oxeno GmbH Paul\u2010Baumann\u2010Stra\u00dfe. 1  Marl Germany"},{"name":"Lehrstuhl F\u00fcr Theoretische Chemie Ruhr\u2010Universit\u00e4t Bochum  Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ralf","family":"Jackstell","sequence":"additional","affiliation":[{"name":"Department of Applied Homogeneous Catalysis Leibniz\u2010Institut f\u00fcr Katalyse e. V. Albert\u2010Einstein\u2010Stra\u00dfe 29a  Rostock Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5709-0965","authenticated-orcid":false,"given":"Matthias","family":"Beller","sequence":"additional","affiliation":[{"name":"Department of Applied Homogeneous Catalysis Leibniz\u2010Institut f\u00fcr Katalyse e. V. 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