Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 24, Pages 9542-9548Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201916410
Keywords
allyl; magnesium; mechanochemistry; polymerization; potassium
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Funding
- National Science Foundation [CHE-1665327]
- ACS-PRF [56027-ND3]
- Charles M. Lukehart Fellowship
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Milling two equivalents of K[1,3-(SiMe3)(2)C3H3] (=K[A ']) with MgX2 (X=Cl, Br) produces the allyl complex [K(2)MgA'(4)] (1). Crystals grown from toluene are of the solvated species [((eta(6)-tol)K)(2)MgA'(4)] ([1.2(tol)]), a trimetallic monomer with both bridging and terminal (eta(1)) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C-C bond lengths differ by only 0.028 angstrom, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an eta(3)-allyl configuration on Mg is energetically preferred over the eta(1)- (sigma-bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1, with activities that are comparable to K[A '] and greater than the homometallic magnesium complex [{MgA '(2)}(2)].
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