Exploring the decomposition pathways of iron asymmetric transfer hydrogenation catalysts.
Exploring the decomposition pathways of iron asymmetric transfer hydrogenation catalysts.
复制标题
探索铁不对称转移加氢催化剂的分解途径。
作者：
Paraskevi O. Lagaditis;Peter E. Sues;A. Lough;R. Morris
本课题组开发了一系列用于还原极性双键的铁基不对称转移氢化（ATH）催化剂。预催化剂的活化以及催化机理已被彻底研究，但这些系统的分解途径知之甚少。在此，我们报告了铁ATH催化剂在催化相关条件下的失活途径的研究。使用实验技术和密度泛函理论（DFT）计算的分解途径进行了研究。形成的主要分解产物Fe（CO）（（Et）2PCH2CH2CHCHNCH2CH2P（Et）2）（3a）和Fe（CO）（（Et）2PCH2CH2C（Ph）C（Ph）NCH2CH2P（Et）2）（3b）在四齿配体的二胺主链上具有两个酰胺供体以及一个C=C键。通过NMR研究鉴定了这些物种，其中一种被分离为与Ru（II）Cp* 的配合物。两个次要的氢化铁物种也形成同时与3a，通过NMR研究，其中之一被分离，并包含一个完全饱和的配体以及氢化物配体。没有发现分离的化合物是活性ATH催化剂。
Our group has developed a series of iron-based asymmetric transfer hydrogenation (ATH) catalysts for the reduction of polar double bonds. The activation of the precatalysts as well as the catalytic mechanism have been thoroughly investigated, but the decomposition pathways of these systems are poorly understood. Herein, we report a study of the deactivation pathways for an iron ATH catalyst under catalytically relevant conditions. The decomposition pathways were examined using experimental techniques and density functional theory (DFT) calculations. The major decomposition products that formed, Fe(CO)((Et)2PCH2CH2CHCHNCH2CH2P(Et)2) (3a) and Fe(CO)((Et)2PCH2CH2C(Ph)C(Ph)NCH2CH2P(Et)2) (3b), had two amido donors as well as a C=C bond on the diamine backbone of the tetradentate ligand. These species were identified by NMR studies and one was isolated as a bimetallic complex with Ru(II)Cp*. Two minor iron hydride species also formed concurrently with 3a, as determined by NMR studies, one of which was isolated and contained a fully saturated ligand as well as a hydride ligand. None of the compounds that were isolated were found to be active ATH catalysts.
影响因子：
15
作者：
Bielinski, Elizabeth A.;Lagaditis, Paraskevi O.;Schneider, Sven
通讯作者：
Schneider, Sven