Project Details
Projekt
Heavy alkali metal amides and phosphides: synthesis, structures, reactivity and catalysis
Applicant
Dr. Felix Krämer
Subject Area
Inorganic Molecular Chemistry - Synthesis and Characterisation
Term
since 2023
Project identifier
Deutsche Forschungsgemeinschaft (DFG) - Project number 535206405
The first subproject focuses on the synthesis of cesium amides (CsNR2) and phosphides (CsPR2) with sterically demanding substituents (-R). Different donor molecules such as crown ethers, oligoamines and cryptands will be used to obtain low-coordinated amide species. The target molecules will be fully characterized by X-ray structural analysis, NMR- as well as IR spectroscopy. Furthermore, the fundamental reactivity in CH-activation of sp2-hybridized substrates such as benzenes, xylenes and naphthalenes will be investigated. These studies are suggested to provide insight into the metallation efficiency, regioselectivity and tolerance to functional groups, solvent selection and stability of the metal intermediates and divulges the full potential of cesium amides as tool in synthetic chemistry. The experimental studies will be supported by quantum chemical calculations to be performed during a residency in Madrid with Prof. Dr. Israel Fernández. Subsequently, the cesium phophides (CsPR2) will be used in the catalytic hydrophosphination reactions of alkynes and alkenes, investigating the influence of the donor molecule on the activity. In the last subproject, the presented cesium (CsNR2) amides are investigated in the transfer hydrogenation of alkenes and alkynes using 1,4-cyclohexadiene. In addition, the potassium and rubidium derivatives will be synthesized and compared with the cesium amides in a systematic study. At this point of the project, a second stay in Madrid is planned to take a closer look at the experimental results from a quantum chemical point of view.
DFG Programme
WBP Fellowship
International Connection
Spain, United Kingdom
