Highly conductive metal–organic frameworks (cMOFs) are formed by incorporating electron-donating fused thiophene rings into their frameworks and extending their π-conjugated systems. The conductivity can be modulated by adjusting the solvent syst...
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Double 1,2‐Carbon Migration at Mixed Heavier Sn=Ge Vinylidenes
Von Wiley-VCH zur Verfügung gestellt
Double 1,2-carbon migration enables the isomerization of the stannagermenylidene to the germastannenylidene. Theoretical studies reveal that the isomerization process involves stepwise carboranyl group and aryl group migration. The reactivity studies demonstrate that the stannagermenylidene undergoes intriguing electron redistribution to give the germylone-stannylene adduct upon treatment with IMe4 and readily reacts with (AlCp*)4 to give the unique heteronuclear aluminyl stannagermyne.
Abstract
1,2-migration is one recurring isomerization reaction in organic chemistry. In contrast, double 1,2-migration remains rare and limited to transition-metal complexes. Herein, we describe the synthesis, characterization and reactivity of mixed heavier Sn=Ge vinylidenes. Double 1,2-carbon migration enables the isomerization of the stannagermenylidene (3) to the germastannenylidene (4). X-ray diffraction analysis and DFT calculations revealed that 3 and 4 feature a Sn=Ge double bond. The reaction of 3 with IMe4 (1,3,4,5-tetramethylimidazoline-2-ylidene) results in the electron redistribution in the Sn=Ge core to give the germylone-stannylene adduct (5). Moreover, treatment of 3 with 0.25 equiv. of (AlCp*)4 produces the heteronuclear aluminyl stannagermyne (6).
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