Optimized Synthesis of Mechanochemically Generated Metal Complexes
Speight, Isaiah Ray
Solvent-based synthesis has been the foundation of chemistry since the inception of synthetic transformations. As chemists become more aware of the chemical and environmental complications that arise from the use and disposal of solvents, new methods have been developed to circumvent these issues, one of which is mechanochemistry. Mechanochemical methods, particularly those involving grinding and milling, have given chemists new tools to utilize in efforts to minimize or avoid solvent use and waste. Circumventing the use of solvents with mechano-chemical methods has also led to advancements in inorganic and organometallic synthesis. An improved preparation of the synthetically important reagent calcium bis(trimethylsilyl)amide, [Ca(N(SiMe3)2], was developed that exploit-ed non-stoichiometric ratios of reagents, and afforded the product in good yield in 10 minutes, free of contaminating calciate species. A mercury(II) imidazolate (Hg(Im)2) framework of square grid (sql) topology was discovered, as well as supporting evidence for C–H···Hg agostic interactions between layers. This species was also the first report-ed example of disappearing polymorphism in a metal-containing species. Advancements to the area of Grignard chemistry were made by the implementation of mechanochemical methods to showcase the activation of carbon-fluorine bonds in homocoupling reactions. Lastly, new ligands for metal allyl compounds that can be utilized in mechanochemical synthesis were investigated. In early results, it was observed that in addition to an improved syn-thesis of a 1,3-tert-butyl substituted allyl precursor, mechanochemistry could also be used at various stages as a solvent-free alternative to the traditional solution-based methods.
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