Cooperative Effects in Iron Catalysts

铁催化剂的协同效应

• 批准号: 228480522
• 负责人: Professor Dr. Robert Langer
• 金额: --
• 依托单位: Arbeitsbereich Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/228480522?language=en
• 关键词: Cooperative; Effects; Iron; Catalysts

With the current project we are aiming to identify construction principles of iron-based pre-catalysts for hydrogenation and dehydrogenation reactions, which are likely leading to the development of more active catalysts. This includes the systematic variation of parameters for a certain combination of ligands, that turns out to result in highly active iron catalysts. In addition to the intended changes in the ligand moiety, which directly influence steric and electronic properties of the corresponding iron complexes, the mode of action of so called cooperative sites is of particular importance. This essential part of the ligand is in most cases an acidic donor group, which is able to provide reversibly a proton. As the variation of this side causes a fundamental change in the reactivity of the corresponding iron complexes, we are aiming to develop a new concept of metal-ligand cooperation, which possibly leads to new catalytic applications. Based on the observed reactivity it seems possible that highly reactive iron fragments can be stabilized be reversible redox steps. These iron fragments are known to react under oxidative addition with many substrates and there reversible stabilization can lead to new catalytic applications and the extension of the concept of metal-ligand cooperation.

通过当前的项目，我们的目标是确定用于加氢和脱氢反应的铁基预催化剂的构造原理，这可能导致更活性催化剂的开发。这包括配体的特定组合的参数的系统变化，这导致高活性的铁催化剂。除了直接影响相应铁络合物的空间和电子性质的配体部分的预期变化之外，所谓的合作位点的作用模式是特别重要的。在大多数情况下，配体的这一必要部分是酸性供体基团，其能够可逆地提供质子。由于这一侧的变化导致相应的铁配合物的反应性发生根本变化，我们的目标是开发一种新的金属-配体合作概念，这可能导致新的催化应用。基于观察到的反应性，似乎可以通过可逆的氧化还原步骤来稳定高反应性的铁片段。已知这些铁片段在氧化加成下与许多底物反应，并且可逆稳定化可以导致新的催化应用和金属-配体合作概念的扩展。

项目成果

Iron-catalyzed hydrogenation and dehydrogenation reactions with relevance to reversible hydrogen storage applications

与可逆储氢应用相关的铁催化加氢和脱氢反应

• DOI: 10.1515/recat-2015-0010
• 发表时间: 2015
• 作者: T. Zell;R. Langer
• 通讯作者: R. Langer

Metal-ligand cooperation in H2 activation with iron complexes bearing hemilabile bis(diphenylphosphino)amine ligands.

带有半不稳定双(二苯基膦)胺配体的铁配合物在H2活化中的金属-配体合作

• DOI: 10.1021/ic5022164
• 发表时间: 2014
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: N. Frank;K. Hanau;R. Langer
• 通讯作者: R. Langer

Ambireactive (R3 P)2 BH2 Groups Facilitating Temperature-Switchable Bond Activation by an Iron Complex.

• DOI: 10.1002/chem.201704018
• 发表时间: 2018-01
• 期刊: Chemistry
• 作者: Lisa Vondung;L. Sattler;R. Langer

Quantifying the Donor Strength of Ligand-Stabilized Main Group Fragments.

• DOI: 10.1021/jacs.9b02598
• 发表时间: 2019-04
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Leon Maser;C. Schneider;Lisa Vondung;Lukas Alig;R. Langer

Selective Hydrogenation of Amides to Amines and Alcohols Catalyzed by Improved Iron Pincer Complexes

• DOI: 10.1021/acs.organomet.6b00251
• 发表时间: 2016-05
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: F. Schneck;Maik Assmann;Markus Balmer;K. Harms;R. Langer