Crucial Role of the Amidine Moiety in Methylenamino Phosphine-Type Ligands for the Synthesis of Tethered η6-Arene-η1-P Ruthenium(II) Complexes: Experimental and Theoretical Studies
| Autor: | Alain Igau, Laure Vendier, Stéphanie Bastin, Jean-Marc Sotiropoulos, Karinne Miqueu, Damien Arquier |
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| Přispěvatelé: | Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Pau et des Pays de l'Adour (UPPA), Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2009 |
| Předmět: |
Steric effects
Coordination sphere Stereochemistry chemistry.chemical_element 010402 general chemistry 01 natural sciences Inorganic Chemistry Amidine Metal chemistry.chemical_compound Moiety [CHIM.COOR]Chemical Sciences/Coordination chemistry Physical and Theoretical Chemistry [CHIM.ORGA]Chemical Sciences/Organic chemistry 010405 organic chemistry Organic Chemistry [CHIM.CATA]Chemical Sciences/Catalysis 0104 chemical sciences Ruthenium [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry [CHIM.POLY]Chemical Sciences/Polymers Molecular geometry chemistry visual_art visual_art.visual_art_medium Phosphine |
| Zdroj: | Organometallics Organometallics, American Chemical Society, 2009, 28 (17), pp.4945-4957. ⟨10.1021/om900231c⟩ |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om900231c |
| Popis: | cited By 12; International audience; Methyleneaminophosphine ligands RZC(Ph)=N-PPh2 (R′ = H (1), Ph (4)) are unable to form tethered η6arene- η1-P ruthenium(II) complexes 3 and 6 starting from their corresponding η1-P metallic precursors 2 and 5. In marked contrast, straightforward high-yield synthesis of tethered η 6arene-η1-P ruthenium(II) complexes 9a,b was achieved upon addition of methylenaminophosphine-type ligands i-Pr2N-C(Ph)=N- PR2 7 (R = Ph (a), i-Pr (b)) on the ruthenium precursor [(pcymene)RuCl2]2 at 80 °C. We have observed by X-ray crystallographic analyses the unprecedented structural adaptive behavior of the N-phosphino amidine ligands 7a,b upon the untethered ηl-P 8a,b or tethered η6-arene-η1-P 9a,b coordination mode in ruthenium(II) complexes. The imino nitrogen atom of the amidine moiety in 7a,b behaves as a "universal joint". In order to minimize the steric hindrance in the second coordination sphere of complexes 8a,b, the value of the Cl-Nl-Pl bond angle of the amidine moiety widened from 119-122° in 7a,b to 133°, which corresponds to a dramatic change in the geometry of the N-phosphino amidine ligands. Moreover, in order to reduce the strain induced by the tethered coordination mode, the value of the Cl-Nl-Pl bond angle in the amidine moiety in ruthenium(II) complexes 9a,b decreases to 116°. DFT calculations have been carried out in order to gain more insight into the structural and electronic properties of the methylenaminophosphine ligands R′-C(Ph)=N-PPh2 as well as the tethered and untethered ruthenium complexes. Moreover, the reaction feasability has also been theoretically discussed. © 2009 American Chemical Society. |
| Databáze: | OpenAIRE |
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