Electron-deficient η1-Indenyl,η3-allylpalladium(II) complexes stabilized by fluxional non-covalent interactions.

Abstract : Highly fluxional, solution-persistent, and formally electron-deficient (32e(-)) binuclear Pd(II)-C(0) complexes of 2-methyl-1H-indene were synthesized and structurally characterized by X-ray diffraction analysis. DFT investigations combined with a number of theoretical analyses of the bond framework suggest that the polar intermetallic interaction possesses no major covalent character. Instead of bearing a static metal-metal bond as suggested by structural X-ray diffraction analysis, the complexes display in solution significant fluxionality through haptotropy, i.e., a formal "oscillation" of the Pd(η(3)-allyl) moiety between two limiting η(1)-indenyl configurations.
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Submitted on : Tuesday, November 19, 2013 - 4:42:05 PM
Last modification on : Tuesday, July 30, 2019 - 8:26:06 AM

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Christophe Werlé, Mustapha Hamdaoui, Corinne Bailly, Xavier-Frédéric Le Goff, Lydia Brelot, et al.. Electron-deficient η1-Indenyl,η3-allylpalladium(II) complexes stabilized by fluxional non-covalent interactions.. Journal of the American Chemical Society, American Chemical Society, 2013, 135 (5), pp.1715-8. ⟨10.1021/ja312003q⟩. ⟨hal-00906414⟩

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