Synthesis and Coordination Chemistry of Pentadienyl Ligands Derived from (1R)-(鈭?-Myrtenal

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• 作者：Ann Christin Fecker ; Bogdan-Florin Cr膬ciun ; Matthias Freytag ; Peter G. Jones ; Marc D. Walter
• 刊名：Organometallics
• 出版年：2014
• 出版时间：July 28, 2014
• 年：2014
• 卷：33
• 期：14
• 页码：3792-3803
• 全文大小：572K
• ISSN：1520-6041

文摘

With the natural product (1R)-(鈭?-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-K鈥?b>3c-K, whose structures were investigated by NMR spectroscopy and X-ray diffraction studies. In all cases a 鈥淯鈥?conformation was observed. Furthermore, the coordination chemistry and electronic properties of these new pentadienyl systems were explored in several half-open trozircene complexes [(畏⁷-C₇H₇)Zr(畏⁵-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.