Metallocene-based Novel Lewis-Pairs; Synthesis, Coordination Behavior, Molecular Activation

基于茂金属的新型路易斯对；

• 批准号: 208319402
• 负责人: Professor Dr. Gerhard Erker
• 金额: --
• 依托单位: Organisch-Chemisches Institut
• 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 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/208319402?language=en
• 关键词: Metallocene; based; Novel; Lewis; Pairs

In the first three year phase of the project we have developed and characterized several active new organometallic frustrated Lewis pairs (omFLPs). These were used for small molecule activation and for the development of e.g. active new hydrogenation catalysts. In the second phase of the project we want to use some of these systems to develop chiral version for application in asymmetric hydrogenation catalysis. We will use terpene and steroid modified bent metallocenes as the stereochemically controlling units in these new systems. In addition we shall use our new approaches to organometallic FLPs for generating novel FLP frameworks and use them in the development of new approaches to catalytic hydroamination (or hydrophosphination) of conjugated dienes or alkynes. Eventually we have planned to use the very robust heteroatom containing members of our new omFLP development for carbon monoxide hydrogenation and coupling. We anticipate that we can find new chemical reactions based on coupling of CO at the omFLP framework with a variety of small molecules including carbon dioxide, another equivalent of CO, sulfur dioxide and even nitric oxide (NO).

在该项目的前三年中，我们已经开发并表征了几个活跃的新有机金属挫败了刘易斯对（OMFLPS）。这些用于小分子激活和例如活跃的新氢化催化剂。在项目的第二阶段，我们希望使用其中一些系统来开发手性版本，以应用于不对称的氢化催化。我们将使用萜烯和类固醇改性的弯曲金属术作为这些新系统中的立体控制单元。此外，我们还将使用我们的新方法来产生新的FLP框架，并将其用于开发共轭二烯或炔烃催化盐水（或水磷酸）的新方法。最终，我们计划使用非常健壮的杂原子，其中包含我们新的OMFLP开发的成员，以进行一氧化碳氢化和耦合。我们预计我们可以在OMFLP框架上与CO的偶联找到新的化学反应，以及各种小分子，包括二氧化碳，二氧化碳，二氧化硫，甚至一氧化氮（NO）的另一种等效物。

项目成果

Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory.

• DOI: 10.1002/chem.201504792
• 发表时间: 2016-03
• 期刊: Chemistry
• 作者: Adrien T. Normand;C. Daniliuc;B. Wibbeling;G. Kehr;Pierre Le Gendre;G. Erker

Zirconocene mediated acetylboron chemistry.

二茂锆介导的乙酰硼化学

• DOI: 10.1039/c8cc02680g
• 发表时间: 2018
• 期刊: Chemical communications
• 影响因子: 4.9
• 作者: Z. Jian;C. G. Daniliuc;G. Kehr;G. Erker
• 通讯作者: G. Erker

The Taming of Redox-Labile Phosphidotitanocene Cations.

氧化还原不稳定的磷酸二茂铁阳离子的驯化

• DOI: 10.1002/chem.201805430
• 发表时间: 2019
• 期刊: Chemistry
• 作者: A. T. Normand;Q. Bonnin;S. Brandès;P. Richard;P. Fleurat-Lessard;C. Devillers;C. Balan;P. Le Gendre;G. Kehr;G. Erker
• 通讯作者: G. Erker