Metalation of dimesitylphosphane oxide, Mes 2 P(O)H ( 1 ), with alkali metal reagents ( n BuLi, NaH, and A(hmds); A = K, Rb, and Cs) in THF yields the corresponding dimesitylphosphinites of lithium ( 2-thf ), sodium ( 3-thf ), potassium ( 4-thf ), rubidium ( 5-thf ), and caesium ( 6 ). Their molecular…
London: The Royal Society of Chemistry, 2024-10-30
The synthesis of ethane-1,2-diyl-bis(diarylphosphane oxides) and -phosphanes, containing bulky ortho -substituted P-bound aryl groups, poses severe challenges, such as drastic reaction conditions and low yields. A potassium base-mediated hydrophosphorylation of phenylacetylene with dimesitylphosphane…
Washington, DC: American Chemical Society, 2024-04-24
Abstract The alkaline‐earth metals Mg and Ca are too inert for the direct metalation of primary and secondary amines. Consequently, activation prior to use is required. Alternatively, the Grignard reagents RMgX (R=alkyl, aryl, X=halide) can be applied in metalation of amines. However, such a straightforward…
Magnesium and calcium are too inert to deprotonate amines directly. For the synthesis of bulky amides alternative strategies are required and in the past, N ‐bound trialkylsilyl groups have been used to ease metalation reactions. The in situ Grignard reagent formation in stirred suspensions of magnesium…
Abstract Alkaline‐earth metalation of dimesitylphosphane oxide Mes 2 P(O)H ( 1 ) in ethereal solvents with dialkylmagnesium and alkylmagnesium bromide as well as the homoleptic bis(trimethylsilyl)amides of calcium, strontium, and barium yields [(L)MgR(μ‐OPMes 2 )] 2 (L/R=thf/Et ( 2‐Et ), Et 2 O/Br (…
The in situ Grignard Metalation Method ( i GMM) is a straightforward one‐pot procedure to quickly produce multigram amounts of Hauser bases R 2 N‐MgBr which are valuable and vastly used metalation reagents and novel electrolytes for magnesium batteries. During addition of bromoethane to a suspension…
The in situ Grignard Metalation Method ( i GMM) is a straightforward one‐pot strategy to synthesize alkaline‐earth metal amides in multi‐gram scale with high yields via addition of bromoethane to an ethereal suspension of a primary or secondary amine and magnesium (Part I) or calcium (Part II). This…
Zielsetzung der Dissertation ist die Etablierung neuer Synthesemethoden zu calciumorganischen Verbindungen. Einfache Zugangangswege vergrößern das Anwendungsfeld dieser, da die Synthesen auch in Laboratorien ausgeführt werden können, die nur eine grundlegende Inert-Arbeitsweise verfolgen. In der metallorganischen…
Abstract In the in situ Grignard metalation method (iGMM), the addition of bromoethane to a suspension of magnesium turnings and cyclopentadienes [C 5 H 6 (HCp), C 5 H 5 ‐Si( i Pr) 3 (HCp TIPS )] in diethyl ether smoothly yields heteroleptic [(Et 2 O)Mg(Cp R )(μ‐Br)] 2 (Cp R =Cp ( 1 ), Cp TIPS ( 2 )).…