Tuning the sterics: Rh-catalyzed hydroformylation reactions with ferrocene based diphosphorus ligands

Dey, Subhayan and Detling, Lea and Gál, Dalma and Bruhn, Clemens and Kelemen, Zsolt and Müller, Christian and Pietschnig, Rudolf (2024) Tuning the sterics: Rh-catalyzed hydroformylation reactions with ferrocene based diphosphorus ligands. JOURNAL OF CATALYSIS, 442. No.-115871. ISSN 0021-9517

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Abstract

The mono- and bidentate ligands FcPPh2 (1), FcPtBu2 (2), FcPMes2 (3), Fc’(PPh2)2 (dppf), Fc’(PMes2)2 (4), Fc’(PMes2)(PPh2) (5), and Fc’(PMes2)(PtBu2) (6) (Fc and Fc’ stand for 1- and 1,1′-substituted ferrocene, respectively) were reacted with Rh(I)-precursors. Maintaining P:Rh stoichiometric ratios of 2:1, dimeric Vaska-type complexes featuring P-Rh-P bridges (7–15), and monomeric complexes with [Rh(CO)2(acac)] moieties (16–22) were obtained. Complexes 16–22 were further applied in the Rh-catalyzed hydroformylation of 1-octene, while the linear-to-branched ratio (l/b) of the formed aldehydes decreases with the increase of steric bulk at the P atoms, which was further verified by theoretical calculations. For ligands 3–5, activation of the C–H bonds of the o-CH3 units of the mesityl substituent occurred with Rh(I), forming complexes with rare five-membered [C3PRh(III)] rings (10, 18a, 20 and 21a). Complexes 8, 10, 11, 13, 15 and 17 were unambiguously characterized by means of single crystal X-ray diffraction.

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