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Synthesis and Coordination Chemistry of Pentadienyl Ligands Derived from (1R)‑(−)-Myrtenal

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posted on 17.12.2015, 03:27 by Ann Christin Fecker, Bogdan-Florin Crăciun, Matthias Freytag, Peter G. Jones, Marc D. Walter
With the natural product (1R)-(−)-myrtenal as the starting material, a series of chiral pentadienes (Pdl*) such as dimethylnopadiene (2a), methylphenylnopadiene (2b), and methylnopadiene (2c) have been prepared by Wittig reactions. Deprotonation with the Schlosser base gives the corresponding potassium pentadienides 3a-K3c-K, whose structures were investigated by NMR spectroscopy and X-ray diffraction studies. In all cases a “U” conformation was observed. Furthermore, the coordination chemistry and electronic properties of these new pentadienyl systems were explored in several half-open trozircene complexes [(η7-C7H7)­Zr­(η5-Pdl*)] and their PMe3 and tBuNC adducts. Density functional theory (DFT) computations are consistent with the experimentally observed face selectivity upon metal coordination: namely, that the metal coordinates exclusively from the sterically less encumbered side.