Carbon-Halogen Bond Activation with Powerful Heavy Alkaline Earth Metal Hydrides

Wiesinger M, Rösch B, Knüpfer C, Mai J, Langer J, Harder S (2021)

Publication Type: Journal article

Publication year: 2021

Journal

DOI: 10.1002/ejic.202100529

Abstract

Reaction of [(^DIPePBDI)SrH]2 with C6H5X (X=Cl, Br, I) led to hydride-halogenide exchange (^DIPePBDI=HC[(Me)CN-2,6-(3-pentyl)phenyl]2). Conversion rates increase with increasing halogen size (FDIPePBDI)SrH]2 with C6H5F was slow and ill-defined but addition of C6H4F2 gave smooth hydride-fluoride exchange. After addition of THF the full range of Sr halogenides was structurally characterized: [(^DIPePBDI)SrX ⋅ THF]2 (X=F, Cl, Br, I). Mixtures of AeN“2 and PhSiH3 in situ formed less defined but more robust Ae metal hydride clusters (AexN”yHz, Ae=Ca, Sr, Ba and N“=N(SiMe3)2) which are able to hydrodefluorinate C6H5F. Conversion rates increase with increasing metal size (Ca2/PhSiH3 mixtures also converted SF6 at room temperature to give undefined decomposition products. Addition of Me6Tren to a SrN“2/PhSiH3 led to crystallization of [Sr6N”2H9 ⋅ (Me6Tren)3⁺][SrN“3⁻]; Me6Tren=tris[2-(dimethylamino)ethyl]amine). After hydrodefluorination, Sr6N”4F8 ⋅ (Me6Tren)2 was formed and structurally characterized. Dissolution in THF led to cluster growth and the larger cluster Sr16N“8F24 ⋅ (THF)12 is structurally characterized. DFT calculations support that hydrodehalogenation of halobenzenes follows a concerted nucleophilic aromatic substitution mechanism (cSNAr).

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How to cite

APA:

Wiesinger, M., Rösch, B., Knüpfer, C., Mai, J., Langer, J., & Harder, S. (2021). Carbon-Halogen Bond Activation with Powerful Heavy Alkaline Earth Metal Hydrides. European Journal of Inorganic Chemistry. https://doi.org/10.1002/ejic.202100529

MLA:

Wiesinger, Michael, et al. "Carbon-Halogen Bond Activation with Powerful Heavy Alkaline Earth Metal Hydrides." European Journal of Inorganic Chemistry (2021).

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