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

在项目的前三年阶段，我们已经开发并表征了几种活性的新型有机金属受挫刘易斯对（omFLPs）。这些被用于小分子活化和开发例如活性的新型加氢催化剂。在项目的第二阶段，我们希望利用这些系统中的一些来开发手性版本，用于不对称氢化催化。我们将使用萜烯和类固醇改性的弯曲茂金属作为这些新体系的立体化学控制单元。此外，我们将使用我们的有机金属FLP的新方法来生成新的FLP框架，并将它们用于开发催化共轭二烯或炔的氢胺化（或氢膦化）的新方法。最终，我们计划将含有新开发的omFLP成员的非常健壮的杂原子用于一氧化碳氢化和偶联。我们期望在omFLP框架下，我们可以发现新的化学反应，基于CO与各种小分子的偶联，包括二氧化碳、CO的另一种当量、二氧化硫甚至一氧化氮（NO）。

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).