The reactivity of phosphagermaallene Mes*P=C=Ge(t -Bu)tip toward aldehydes and ketones: An experimental and theoretical study - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2010

The reactivity of phosphagermaallene Mes*P=C=Ge(t -Bu)tip toward aldehydes and ketones: An experimental and theoretical study

Résumé

Phosphagermaallene Mes*P=C=Ge(t-Bu)Tip 1 (Tip = 2,4,6- triisopropylphenyl, Mes* = 2,4,6-tri-tert-butylphenyl) has been obtained by an improved synthesis in relation to the previously reported preparation starting from t-BuGeCl3. Very short Ge=C (1.761(2) Å) and P=C (1.625(2) Å) double bond lengths, trigonal planar geometry around the Ge atom, and GeCP bond angle of 166.57° are indicative of an heteroallenic structure for 1. Its reactions with crotonaldehyde and cinnamaldehyde lead to 1-oxa-2-germacyclobutanes by a [2 + 2] cycloaddition between the Ge=C and C=O double bonds; with methyl vinyl ketone, both a [2 + 4] cycloaddition between the Ge=C and the O=C-C=C moieties and an ene-reaction are observed leading to a 1-oxa-2-germacyclohex-5-ene and a germyl(butadienyl)ether, respectively. With acetophenone, an ene-reaction occurs to afford exclusively a germyl(vinyl)ether. DFT calculations have been performed to explain the regiochemistry observed. © 2010 American Chemical Society.
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Dates et versions

hal-01613253 , version 1 (09-10-2017)

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F. Ouhsaine, E. André, Jean-Marc Sotiropoulos, J. Escudie, H. Ranaivonjatovo, et al.. The reactivity of phosphagermaallene Mes*P=C=Ge(t -Bu)tip toward aldehydes and ketones: An experimental and theoretical study. Organometallics, 2010, 29 (11), pp.2566-2578. ⟨10.1021/om100233y⟩. ⟨hal-01613253⟩
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