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.