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 - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2009

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

Résumé

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.
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Dates et versions

hal-01613255 , version 1 (09-10-2017)

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D. Arquier, Laure Vendier, Karinne Miqueu, Jean-Marc Sotiropoulos, S. Bastin, et al.. 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. Organometallics, 2009, 28 (17), pp.4945-4957. ⟨10.1021/om900231c⟩. ⟨hal-01613255⟩
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