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Home » Long Group Published in Chem. Eur. J.

Long Group Published in Chem. Eur. J.

Long Group Published in Chem. Eur. J.

April 15, 2021 by Kayla Benson

The Long Group published their research “Mechanochemical Formation, Solution Rearrangements, and Catalytic Behavior of a Polymorphic Ca/K Allyl Complex” in Chemistry—A European Journal. Authors Brian Long and Alicia Doerr, graduate student, collaborated with Vanderbilt University and the University of Rochester. 

Without solvents present, the often far‐from‐equilibrium environment in a mechanochemically driven synthesis can generate high‐energy, non‐stoichiometric products not observed from the same ratio of reagents used in solution. Ball milling 2 equiv. K[A´] (A´ = [1,3‐(SiMe3)2C3 H3]– ) with CaI2  yields a non‐stoichiometric calciate, K[CaA´3], which initially forms a structure (1) likely containing a mixture of pi‐ and sigma‐bound allyl ligands. Dissolved in arenes, the compound rearranges over the course of several days to a structure (2) with only  η3‐bound allyl ligands, and that can be crystallized as a coordination polymer. If dissolved in alkanes, however, the rearrangement of 1 to 2 occurs within minutes. The structures of 1 and 2 have been modeled with DFT calculations, and 2 initiates the anionic polymerization of methyl methacrylate and isoprene; for the latter, under the mildest conditions yet reported for a heavy Group 2 species (one‐atm pressure and room temperature).

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Filed Under: Artsci, Long, News, Polymer Chemistry

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