Salicylaldimines: Formation via Ring Contraction and Synthesis of Mono- and Heterobimetallic Alkali Metal Heterocubanes

The formation of salicylaldimine derivatives via ring contraction as byproducts in 2-aminotropone syntheses has been investigated. Salicylaldiminate (SAI) complexes of the alkali metals Li-K have been synthesized and transformed into heterobimetallic complexes. Important findings include an unusual double heterocubane structure of the homometallic sodium SAI, an unprecedented ligand-induced E/Z isomerization of the aldimine functional group in the homometallic potassium SAI, and the first example of a structurally authenticated mixed-metal SAI based on s-block central atoms. Rapid equilibria have been shown to play a crucial role in the solution phase chemistry of mixed-metal SAIs. Analytical techniques applied in this work include (heteronuclear) NMR spectroscopy, VT- and DOSY NMR spectroscopy, high-resolution mass spectrometry, single-crystal X-ray diffraction analysis, and DFT calculations.