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Highly Active Hydroformylation Catalysts: Synthesis, Characterisation and Catalytic Performance

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Abstract

The phoszone ligand [(Ph2P)(bis-3,5-CF3-Ph)]NN=CH(penta-fluoro-Ph) transformed in liquid CO2 at room temperature in presence of [Rh(cod)2]OTf into [Rh(cod)(η2-P,P′-Ph2POPPh2)]OTf. Replacing the O-atom in Ph2POPPh2 by a PrN-group leads to the ligand PrN(PPh2)2 acting similarly as a bidentate ligand in [Rh(cod)(η2-P,P′-PrN(PPh2)2)]OTf. Hydroformylation of 1-octene with in situ catalysts formed by the ligands with [Rh(cod)2]OTf showed hydroformylation activities at 50 % conversion of 16,000 h−1 (PrN(PPh2)2/[Rh(cod)2]OTf) and 24,000 h−1 (phoszone/[Rh(cod)2]OTf), respectively.

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Notes

  1. Structural details for 2*OTf: Reflections collected/unique/observed (I > 2σ): 40,467/15,873/12,529 [R(int) = 0.222]; parameters refined: 800; formula C66H65F6O8P4Rh2S2 (two molecules), MM per molecule 747.0 g/mol; T = 200(2) K; triclinic, P-1 (No. 2, Z = 2); a = 1,149.5(1) pm; b = 1,515.5(1) pm; c = 2,049.6(2) pm; α = 71.784(1)°; β = 78.518(1)°; γ = 70.494(1)°; V = 3,179.2(5) × 106 pm3; ρ (calc.) = 1.561 g/cm3; Absorption coefficient = 0.758 mm−1; F(000) = 1,522; Goof (F2) = 1.035; crystal size = 0.8 × 0.8 × 0.6 mm3; index ranges −16 < h < 16, −21 < k < 20, −28 < l < 28; completeness to θ = 28.34: 95.2 %; R1 (I > 2σ) = 0.0316, wR2 = 0.0851 (all data), largest difference peak and hole: 0.836 and −0.513 × 10−6 pm−3. Structural details for 4*OTf*CDCl3: Reflections collected/unique/observed: 25,128/9,067/8,250 [R(int) = 0.0317]; parameters refined: 467; formula C37H40Cl3F3NO3P2RhS, MM 906.96 g/mol; T = 200(2) K; monoclinic, Pn (No. 7, Z = 2); a = 1,158.8(3) pm; b = 944.1(3) pm; c = 1,815.7(5) pm; β = 105.465(5)°; V = 1,914(1) × 106 pm3; ρ (calc.) = 1.573 g/cm3; Absorption coefficient = 0.846 mm−1; F(000) = 924; Goof (F2) = 1.014; crystal size = 0.6 × 0.6 × 0.5 mm3; index ranges −15 < h < 15, −12 < k < 12, −24 < l < 24; completeness to θ = 28.34: 97.7%; R1 (I > 2σ) = 0.0307 wR2 = 0.0698 (all data), largest difference peak and hole: 0.653 and −0.325 × 10−6 pm−3.

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Acknowledgment

The authors would like to express their deepest thanks to the KIT and the ETH Zürich for the financial and Prof. Dr. Eckhard Dinjus for the general support of this work.

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Authors and Affiliations

  1. IKFT, Campus Nord, KIT, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

    Elisabetta Piras, Bernhard Powietzka, Frederik Wurst, Doreen Neumann-Walter, Thomas Otto, Thomas Zevaco & Olaf Walter

  2. Laboratorium für Anorganische Chemie, Wolfgang-Pauli-Street. 10, ETH Hönggerberg, HCI H 131, 8093, Zurich, Switzerland

    Elisabetta Piras & Hans-Jörg Grützmacher

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  1. Elisabetta Piras
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Correspondence to Olaf Walter.

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Dedicated to the memory of Prof. Ivano Bertini.

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Piras, E., Powietzka, B., Wurst, F. et al. Highly Active Hydroformylation Catalysts: Synthesis, Characterisation and Catalytic Performance. Catal Lett 143, 673–680 (2013). https://doi.org/10.1007/s10562-013-1010-x

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