The reactions of chlorogermylene MsFluind tBu-GeCl 1, supported by a sterically encumbered hydrindacene ligand MsFluind tBu, with NaPCO­(dioxane)2.5 and NaAsCO­(18-c-6) in the presence of trimethylphosphine afforded trimethylphosphine-stabilized germylidenyl-phosphinidene 2 and -arsinidene 3, respectively. Structural and computational investigations reveal that the Ge–E′ bond (E′ = P and As) features a multiple-bond character. 2 and 3 exhibit diverse reactivity toward trimethylsilylacetylene and 4-tetrabutylphenylacetylene. Specifically, 2 underwent cycloadditions with both alkynes affording the first six-membered aromatic phosphagermabenzen-1-ylidenes 4 and 5, respectively, through the heavier isocyanide intermediate MsFluind tBu-PGe. In contrast, 3 could serve as a synthetic equivalent of heavier isocyanides and nitriles when treated with trimethylsilylacetylene and 4-tetrabutylphenylacetylene yielding arsagermene 6 and arsolylgermylene 7, respectively. The reaction mechanisms for the cycloadditions were investigated through density functional theory calculations. The reactivity studies highlight the potential of 2 and 3 in accessing heavy main-group element-containing heterocycles.

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The reaction of the carbazole ligand supported Ga(I) compound LGa(THF) (3) and 1-azido-4-(tert-butyl)benzene (ArN3) afforded the first stable tetrazagallole LGaN4Ar2 (4) bearing a three-coordinate Ga atom. Reduction of 4 with...

The first germanimidoyl chloride MsFluindtBu-Ge(Cl)=NMes (2, where MsFluindtBu is a bulky hydrindacene skeleton) was synthesized through the reaction of MsFluindtBu-GeCl (1) and mesityl azide (MesN3). Contrastingly, treatment of 1 with...