Halide metathesis in overdrive: Mechanochemical synthesis of a heterometallic group 1 allyl complex

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Abstract

As a synthesis technique, halide metathesis (n RM + M'Xn → RnM' + n MX) normally relies for its effectiveness on the favorable formation of a metal halide byproduct (MX), often aided by solubility equilibria in solution. Owing to the lack of significant thermodynamic driving forces, intra-alkali metal exchange is one of the most challenging metathetical exchanges to attempt, especially when conducted without solvent. Nevertheless, grinding together the bulky potassium allyl [KA']∞ (A' = [1,3-(SiMe3)2C3H3]–) and CsI produces the heterometallic complex [CsKA'2]∞ in low yield, which was crystallographically characterized as a coordination polymer that displays site disorder of the K+ and Cs+ ions. The entropic benefits of mixed Cs/K metal centers, but more importantly, the generation of multiple intermolecular K…CH3 and Cs…CH3 interactions in [CsKA'2]∞, enable an otherwise unfavorable halide metathesis to proceed with mechanochemical assistance. From this result, we demonstrate that ball milling and unexpected solid-state effects can permit seemingly unfavored reactions to occur.

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Koby, R. F., Rightmire, N. R., Schley, N. D., Hanusa, T. P., & Brennessel, W. W. (2019). Halide metathesis in overdrive: Mechanochemical synthesis of a heterometallic group 1 allyl complex. Beilstein Journal of Organic Chemistry, 15, 1856–1863. https://doi.org/10.3762/bjoc.15.181

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