Cyclopentadienylalkylphosphide Chelate Complexes

• Applicant: Professor Dr. Holger Butenschön
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation ; Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2011 to 2020
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 201033285

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.

• DFG Programme: Research Grants