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Starting from the extensive application MOFs as Lewis acid and Lewis base catalysts, this article uses catalytic hydrogenation to briefly summarize the efforts made to heterogenize boron and amine in MOFs to mimic molecular FLP systems. The core of this concept is based on recent findings which demonstrate the ability of two commonly used MOFs, namely UiO\u201066 and MIL\u2010101, to catalyze the selective hydrogenation of polar double X=Y bonds at moderate H<jats:sub>2<\/jats:sub> pressures below 10\u2005bar. The influence of electron\u2010donating, the withdrawal of substituents on the linker, and the aniline poisoning effect highlight the significance of Lewis acid sites, while density\u2010functional theory calculations indicate the heterolytic H\u2212H bond cleavage at the MOF metal oxo clusters. It is expected that this new perspective on MOFs as solid FLP systems will spur further research to explore and define the potential of dual sites in the catalytic activation of small molecules.<\/jats:p>","DOI":"10.1002\/chem.202204016","type":"journal-article","created":{"date-parts":[[2023,5,2]],"date-time":"2023-05-02T13:17:48Z","timestamp":1683033468000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":23,"title":["New Opportunities in Metal\u2010Organic Framework Catalysis: From Bifunctional to Frustrated Lewis Pairs Catalysis"],"prefix":"10.1002","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0991-6608","authenticated-orcid":false,"given":"Amarajothi","family":"Dhakshinamoorthy","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica Universitat Polit\u00e8cnica de Val\u00e8ncia  Camino de Vera, s\/n 46022 Valencia Spain"},{"name":"School of Chemistry Madurai Kamaraj University  Madurai 625021 Tamil Nadu India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7905-3209","authenticated-orcid":false,"given":"Abdullah M.","family":"Asiri","sequence":"additional","affiliation":[{"name":"Center of Excellence in Advanced Materials Research King Abdulaziz University  Jeddah Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9664-493X","authenticated-orcid":false,"given":"Hermenegildo","family":"Garcia","sequence":"additional","affiliation":[{"name":"Center of Excellence in Advanced Materials Research King Abdulaziz University  Jeddah Saudi Arabia"},{"name":"Instituto Universitario de Tecnolog\u00eda Qu\u00edmica Consejo Superior de Investigaciones Cient\u00edficas Universitat Politecnica de Valencia  Av. 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