Richardson Georgia M, Douair Iskander, Cameron Scott A, Maron Laurent, Anker Mathew D
School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington, New Zealand.
LPCNO, CNRS ( INSA, Université Paul Sabatier, Université de Toulouse et CNRS, 135 Avenue de Rangueil, 31077, Toulouse, France.
Chemistry. 2021 Sep 15;27(52):13144-13148. doi: 10.1002/chem.202102428. Epub 2021 Jul 30.
A dimeric β-diketiminato ytterbium(II) hydride affects both the two-electron aromatization of 1,3,5,7-cyclooctatetraene (COT) and the more challenging two-electron reduction of polyaromatic hydrocarbons, including naphthalene (E =-2.60 V). Confirmed by Density Functional Theory calculations, these reactions proceed via consecutive polarized Yb-H/C=C insertion and deprotonation steps to provide the respective ytterbium (II) inverse sandwich complexes and hydrogen gas. These observations highlight the ability of a simple ytterbium(II) hydride to act as a powerful two-electron reductant at room temperature without the necessity of an external electron to initiate the reaction and avoiding radicaloid intermediates.
一种二聚β-二酮亚胺基氢化镱（II）既影响1,3,5,7-环辛四烯（COT）的双电子芳构化，也影响多环芳烃更具挑战性的双电子还原，包括萘（E = -2.60 V）。经密度泛函理论计算证实，这些反应通过连续的极化Yb-H/C=C插入和去质子化步骤进行，以生成相应的镱（II）反夹心配合物和氢气。这些观察结果突出了一种简单的氢化镱（II）在室温下作为强大双电子还原剂的能力，无需外部电子引发反应，且避免了类自由基中间体。
