Cyclopentadienylalkylphosphide Chelate Complexes

在第一期项目成果的基础上，将进一步研究含二磷基团的环戊二烯烷基膦配合物的反应性。为了达到这个目的，二级磷化基团将被去质子化，使卤化物配体解配，同时与电中性配体络合。接下来，卤化物配体将通过路易斯酸的方法去配位，并且通过电中性配体的络合也将生成环戊二烯烷基磷化物络合物。使用受挫的刘易斯酸碱对（FLPs）可以一步去除卤化物并协调FLP磷化功能。此外，将研究与炔基阴离子的反应，特别是与（2-吡啶基）乙基阴离子的反应，以便通过硅基或氢化物迁移生成偏二或丙二体系。最后，将开发催化反应，与传统的过渡金属催化不同，它不是由一系列氧化添加和还原消除组成，而是保持金属的氧化状态。作为一个例子，烷基的硅氢化反应将首先在这种情况下进行研究。最后，所获得的结果将被配体系统和过渡金属的变化所推广。

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.