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Secondary Phosphane Oxides as Preligands in Rhodium-Catalyzed Hydroformylation

Authors

  • Dr. Andrea Christiansen,

    1. Leibniz-Institut für Katalyse an der Universität Rostock e.V. A.-Einstein-Str. 29a, 18059 Rostock (Germany), Fax: (+49) 381-1281-51202
    2. Evonik Oxeno GmbH, Paul-Baumann-Str. 1, 45772 Marl (Germany)
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  • Dr. Chuanzhao Li,

    1. Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore, 627833 (Singapore)
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  • Dr. Marc Garland,

    1. Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore, 627833 (Singapore)
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  • Dr. Detlef Selent,

    1. Leibniz-Institut für Katalyse an der Universität Rostock e.V. A.-Einstein-Str. 29a, 18059 Rostock (Germany), Fax: (+49) 381-1281-51202
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  • Prof. Dr. Ralf Ludwig,

    1. Leibniz-Institut für Katalyse an der Universität Rostock e.V. A.-Einstein-Str. 29a, 18059 Rostock (Germany), Fax: (+49) 381-1281-51202
    2. Institut für Chemie der Universität Rostock, A.-Einstein-Str. 3a, 18059 Rostock (Germany)
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  • Dr. Robert Franke,

    1. Evonik Oxeno GmbH, Paul-Baumann-Str. 1, 45772 Marl (Germany)
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  • Prof. Dr. Armin Börner

    1. Leibniz-Institut für Katalyse an der Universität Rostock e.V. A.-Einstein-Str. 29a, 18059 Rostock (Germany), Fax: (+49) 381-1281-51202
    2. Institut für Chemie der Universität Rostock, A.-Einstein-Str. 3a, 18059 Rostock (Germany)
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Abstract

Four aryl-substituted secondary phosphane oxides (SPOs) were tested as preligands in the rhodium catalyzed hydroformylation of cyclohexene and 1-octene. Three of them form active hydroformylation catalysts through their phosphinous acid tautomers. n-Regioselectivities of up to 56 % were achieved in the reaction with the linear olefin. The catalytic system with the electron-poor SPO showed exceptional behavior. In situ high-pressure IR spectroscopic investigations accompanied by DFT calculations provide an explanation of the observed inhibition of the catalytic reaction. Furthermore, proof is given that noncoordinated SPOs readily react with product aldehydes at room temperature to form α-hydroxyphosphinic acids. In contrast Rh-catalyzed hydrophosphination did not take place.

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