Phosphine containing dendrimers for highly regioselective rhodium catalysed hydroformylation of alkenes: a positive ‘dendritic effect’
- 1 November 2002
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 23,p. 4323-4334
- https://doi.org/10.1039/b206597e
Abstract
Diphenylphosphine functionalised polyhedral oligomeric silsesquioxane (POSS) dendrimers are used as ligands for the rhodium catalysed hydroformylation of oct-1-ene showing unexpectedly high regioselectivity to the linear aldehyde nonan-1-al (l ∶ b = 14 ∶ 1). Comparative studies with the small molecule analogues, bis-diphenylphosphinopentane, Me2Si[CH2CH2PPh2]2 and Si[CH2CH2PPh2]4, clearly confirm the unusual selectivity of these bidentate dendritic ligands and show that a ‘positive dendritic effect’ occurs. This high selectivity is obtained with only one structure within the 1st and 2nd generation dendrimer (spacer of five atoms between the phosphorus atoms, and carbon–silicon linkage) whilst other frameworks (spacer of three and seven atoms between the P atoms, or carbon–oxygen–silicon linkage) lead to lower selectivity.Keywords
This publication has 42 references indexed in Scilit:
- Transition Metal Catalysis Using Functionalized DendrimersAngewandte Chemie International Edition in English, 2001
- Cooperative Asymmetric Catalysis with Dendrimeric [Co(salen)] ComplexesPublished by Wiley ,2000
- Cross-Linked Scandium-Containing Dendrimers: A New Class of Heterogeneous CatalystsAngewandte Chemie International Edition in English, 2000
- The “Dendritic Effect” in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts: Observation of Active-Site Proximity Effects in Atom-Transfer Radical AdditionAngewandte Chemie International Edition in English, 2000
- Selective Hydrovinylation of Styrene in a Membrane Reactor: Use of Carbosilane Dendrimers with Hemilabile P,O LigandsAngewandte Chemie International Edition in English, 1999
- Allylic Substitution with Dendritic Palladium Catalysts in a Continuously Operating Membrane ReactorJournal of Catalysis, 1999
- Bimetallic Hydroformylation Catalysis: In Situ Characterization of a Dinuclear Rhodium(II) Dihydrido Complex with the Largest Rh–HNMR Coupling ConstantAngewandte Chemie International Edition in English, 1996
- A study of the mechanism of rhodium/phosphine-catalyzed hydroformylation: use of 1,1′-bis(diarylphosphino)ferrocene ligandsJournal of Molecular Catalysis, 1982
- Oligophosphin-Liganden, I. Einfache Synthesen der trimethylenverknüpften Triphosphine RP[(CH2)3PPh2]2 und ihrer Vorstufen Ph2P(CH2)3P(H)R (R = Ph, Me) / Oligophosphine Ligands, I Convenient Syntheses of the Trimethylene-linked TriphosphinesRP[(CH2)3PPh2]2 and their Precursors Ph2P(CH2)3P(H)R (R = Ph, Me)Zeitschrift für Naturforschung B, 1980
- Phosphinomethyllithium compounds IV. An improved method of preparation and some synthetic applicationsJournal of Organometallic Chemistry, 1967