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Acceptorless Alcohol Dehydrogenation: OH vs NH Effect in Bifunctional NHC–Ir(III) Complexes

Cite this: Organometallics 2018, 37, 5, 636–644
Publication Date (Web):May 18, 2017
https://doi.org/10.1021/acs.organomet.7b00220
Copyright © 2017 American Chemical Society

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    Abstract

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    Bifunctional complexes bearing N-heterocyclic carbene (NHC) ligands functionalized with hydroxy or amine groups were synthesized to measure the beneficial effect of different modes of metal–ligand cooperation in the acceptorless dehydrogenation of alcohols. In comparison to complexes with an amine moiety, hydroxy-functionalized iridium catalysts showed superior activity. In contrast to alcohols, 1,4-diols underwent cyclization to give the corresponding tetrahydrofurans without involving dehydrogenation processes. Mechanistic investigations to rationalize the “OH effect” in these types of complexes have been undertaken.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.7b00220.

    • Experimental details, 1H NMR and 13C NMR spectra, kinetic data, and crystallographic data (PDF)

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    CCDC 1509620 and 15316081531609 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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