Transition-Metal Oxos as the Lewis Basic Component of Frustrated Lewis Pairs

The reaction of oxorhenium complexes that incorporate diamidopyridine (DAP) ligands with B­(C6F5)3 results in the formation of classical Lewis acid–base adducts. The adducts effectively catalyze the hydrogenation of a variety of unactivated olefins at 100 °C. Control reactions with these complexes o...

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Published inJournal of the American Chemical Society Vol. 138; no. 14; pp. 4832 - 4842
Main Authors Lambic, Nikola S, Sommer, Roger D, Ison, Elon A
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 13.04.2016
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Summary:The reaction of oxorhenium complexes that incorporate diamidopyridine (DAP) ligands with B­(C6F5)3 results in the formation of classical Lewis acid–base adducts. The adducts effectively catalyze the hydrogenation of a variety of unactivated olefins at 100 °C. Control reactions with these complexes or B­(C6F5)3 alone did not yield any hydrogenated products under these conditions. Mechanistic studies suggest a frustrated Lewis pair is generated between the oxorhenium DAP complexes and B­(C6F5)3, which is effective at olefin hydrogenation. Thus, we demonstrate for the first time that the incorporation of a transition-metal oxo in a frustrated Lewis pair can have a synergistic effect and results in enhanced catalytic activity.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b00705