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    Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex

    Sung, Simon and Boon, Jie Kang and Lee, Johnathan J.C. and Rajabi, Nasir A. and Macgregor, Stuart A. and Krämer, Tobias and Young, Rowan D. (2017) Convergent (De)Hydrogenative Pathways via a Rhodium α-Hydroxylalkyl Complex. Organometallics, 36 (8). pp. 1609-1617. ISSN 0276-7333

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    We report the convergent reaction pathways between [RhH(PPh3)4] and POP ketone (1) and alcohol (2) ligands that terminate in the formation of an α-hydroxylalkyl rhodium(I) complex (3), representing two halves of a formal reduction/oxidation pathway between 1 and 2. In the case of hydride transfer to 1, the formation of the α-hydroxylalkyl rhodium(I) complex (3) proceeds via a rare hydrido(η2-carbonyl) complex (4). C–H activation in 2 at the proligand’s central methine position, rather than O–H activation of the hydroxy motif, followed by loss of dihydrogen also generates the α-hydroxylalkyl rhodium(I) complex (3). The validity of the postulated reaction pathways is probed with DFT calculations. The observed reactivity supports α-hydroxylalkyl complexes as competent intermediates in ketone hydrogenation catalyzed by rhodium hydrides and suggest that ligands 1 and 2 may be “noninnocent” coligands in reported hydrogenation catalyst systems in which they are utilized.

    Item Type: Article
    Keywords: Homogeneous Hydrogenation; Synthesis GAS; Carbon Monoxide; Metallacyclic Manganese; Hydroxyalkyl Complexes; Ruthenium Complexes; Chemistry, Organic; Mechanistic Insight; Noncovalent Interactions; Tropsch Type Reactions; Reductive Elimination; Chemistry, inorganic & nuclear;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 11593
    Identification Number:
    Depositing User: Tobias Kraemer
    Date Deposited: 04 Nov 2019 15:00
    Journal or Publication Title: Organometallics
    Publisher: American Chemical Society
    Refereed: Yes
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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