Cyclopentadienylalkylphosphide Chelate Complexes

在第一阶段研究成果的基础上，将进一步研究合成的含仲膦结构的环戊二烯基烷基膦配合物的反应活性。为了实现这一点，仲膦烷基将被去质子化，从而提供卤化物配体的解离与电子中和配体的同时络合。下一步，卤化物配体将通过Lewis酸解配位，通过电子中和配体的络合，还将生成环戊二烯基烷基膦络合物。使用受挫的Lewis酸碱对(FLP)将允许在一步中去除卤化物并协调FLP膦功能。此外，还将研究与炔基阴离子，特别是(2-吡啶基)乙炔阴离子的反应，以便通过硅基或氢化物迁移生成亚乙烯或烯丙叉体系。与传统的过渡金属催化不同，它不是由一系列的氧化加成和还原消除组成，而是保持金属的氧化状态。作为一个例子，将首先在此背景下研究炔烃的硅氢化反应。最终，所获得的结果将通过配位体系统和过渡金属的变化来推广。

Based on the results achieved in the first project phase, the reactivity of the cyclopentadienylalkylphosphane complexes prepared bearing a secondary phosphane moiety will further be investigated. To accomplish this, the secondary phosphane groups will be deprotonated affording a decomplexation of a halide ligand with simultaneous complexation of an electroneutral ligand. Next, halide ligands will be de-coordinated by means of Lewis acids, and by complexation of an electroneutral ligand a cyclopentadienylalkylphosphide complex will be generated as well. Using frustrated Lewis acid base pairs (FLPs) will allow to remove a halide and to coordinate the FLP phosphane function in one step. In addition, reactions with alkynyl anions, particularly (2-pyridyl)ethynyl anions, will be investigated in order to generate vinylidene or allenylidene systems by silyl or hydride migration. Finally, catalytic reactions will be developed, which in contrast to conventional transition metal catalysis are not composed by a sequence of oxidative additions and reductive eliminations, but maintain the oxidation state of the metal. As an example, the hydrosilylation of alkynes will first be investigated in this context. Eventually, the results achieved will be generalized by variations of the ligand systems and the transition metal.