Mixed metal multinuclear Cr(III) cage compounds and coordination polymers based on unsubstituted phenolate: design, synthesis, mechanism, and properties

Crochet, Aurélien; Brog, Jean-Pierre; Fromm, Katharina M.

doi:10.1021/acs.cgd.5b01084

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Journal article

Mixed metal multinuclear Cr(III) cage compounds and coordination polymers based on unsubstituted phenolate: design, synthesis, mechanism, and properties

Crochet, Aurélien Department of Chemistry & Fribourg Center for Nanomaterials, University of Fribourg, Switzerland
Brog, Jean-Pierre Department of Chemistry & Fribourg Center for Nanomaterials, University of Fribourg, Switzerland
Fromm, Katharina M. Department of Chemistry & Fribourg Center for Nanomaterials, University of Fribourg, Switzerland

06.01.2016

Published in:

Crystal Growth & Design. - 2016, vol. 16, no. 1, p. 189–199

English Oxidative substitution reactions of chromium(II) chloride with lithium phenoxide in the presence of water give access to new polynuclear chromium(III) aryloxide complexes and coordination polymers. While a one-dimensional coordination polymer based on chromium(III), [Cr₂(μ₃-OPh)₂(μ-OPh)₆(μ-OH)(μ₃-Li)₄(μ₃-Cl)₂Li(THF)₆]_n, is first obtained by serendipity, the controlled addition of water to the initial Cr(II) complex as well as variation of the stoichiometry lead to three new discrete chromium(III) aggregates, namely, [Cr(OPh)₄(μ-OH)Li₂(THF)₃]₂, [Cr₃Li₃(OPh)₉(μ₃-OH)(μ₃-O)(THF)₆], and [Cr₄(μ-OPh)₈(μ₃-OH)₆(μ-OH)₂Cl₂Li₆(THF)6]·2THF. The use of deuterated species allowed confirmation of the oxidation based on the addition of water by detection of H₂, HD, and D₂. During these investigations, we have also identified a THF-adduct of chromium(II) chloride, [CrCl₂(THF)₂], used in the literature as a precursor in numerous syntheses, but with a hitherto unknown structure.

Faculty

Faculté des sciences et de médecine

Department

Département de Chimie

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