Abstract
Despite the notable progress in aluminium chalcogenides, their sulfur congeners have rarely been isolated under mild conditions owing to limited synthetic precursors and methods. Herein, facile isolation of diverse molecular aluminium sulfides is achievable, by the reaction of N‐heterocyclic carbene‐stabilized terphenyl dihydridoaluminium (1) with various thiation reagents. Different to the known dihydridoaluminium 1Tipp , 1 features balanced stability and reactivity at the Al center. It is this balance that enables the first monomeric aluminium hydride hydrogensulfide 2, the six‐membered cyclic aluminium polysulfide 4 and the five‐membered cyclic aluminium polysulfide 6 to be isolated, by reaction with various equivalents of elemental sulfur. Moreover, a rare aluminium heterocyclic sulfide with Al−S−P five‐membered ring (7) was obtained in a controlled manner. All new compounds were fully characterized by multinuclear NMR spectroscopy and elemental analysis. Their structures were confirmed by single‐crystal X‐ray diffraction studies.
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