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- W2030717368 abstract "The heterodimetallic compound [(Me3Si)2NMg{μ-N(SiMe3)2}2CaN(SiMe3)2], 3, can be prepared as single-component crystals through manipulation of the equilibrium established on mixing the homometallic derivatives Mg[N(SiMe3)2]2, 1, and Ca[N(SiMe3)2]2, 2, in toluene/hexane solution. Specifically, doping solutions with a 30% molar excess of 1 is required in order to avoid cocrystallization with 2. Complex 3 has been characterized by single-crystal X-ray diffraction and multinuclear NMR spectroscopy and is found to adopt a heterodimetallic Mg(μ2-N)2Ca ring structure in the solid state and in arene solutions. DFT computational studies confirm the experimentally observed variations in the metrical parameters between the homo- and heterodimetallic complexes. The calculations also indicate that the reaction to form 3 is close to being thermoneutral. Addition of pyridine to 3 results in asymmetric cleavage of the mixed-metal ring structure, in turn forming a kinetically stable, charge-separated “ate” species of the type [(Me3Si)2NCa·(pyr)n]+[Mg{N(SiMe3)2}3]-, 4. The three bases 1, 2, and 4 react with propiophenone in pyridine media at ambient temperature to give high Z stereoselectivities of ≥98%." @default.
- W2030717368 created "2016-06-24" @default.
- W2030717368 creator A5028353874 @default.
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- W2030717368 creator A5077854615 @default.
- W2030717368 creator A5050205783 @default.
- W2030717368 date "2006-09-07" @default.
- W2030717368 modified "2023-10-03" @default.
- W2030717368 title "Heterodimetallic Alkaline Earth Metal Amides: Synthesis, Structure, and Solvent-Induced Charge Separation of Homoleptic Calcium−Magnesium Hexamethyldisilazide" @default.
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