Synthesis of a Diamido‐Germylene from an Inorganic Cumulene

The advent of boron‐containing cumulenes as carbodiimide analogs allows for the one‐pot synthesis of low‐valent main‐group species stabilized by a dianionic bis(borylamido) ligand chelate. Here, the synthesis and characterization of germylene complexes accessed via the reaction of GeCl 2 ·dioxane with K[(HCDippN) 2 BNBNB(NDippCH) 2 ] (K[(boryl)NBN(boryl)], 1 ) is reported. The four‐membered N‐heterocyclic germylene [ClB{(boryl)N} 2 ]Ge ( 2‐Cl ) generated reacts further with 1,3,4,5‐tetramethylimidazol‐2‐ylidene (IMe 4 ) to yield the structurally characterized Ge‐bound adduct [ClB{(boryl)N} 2 ]Ge·IMe 4 ( 3‐Cl ). Reaction with trimethylsilyl azide (Me 3 SiN 3 ) then affords the related azido‐functionalized system [(N 3 )B{(boryl)N} 2 ]Ge·IMe 4 ( 3‐N 3 ). Density functional theory and natural bond orbital analyses of 2‐Cl reveal a greater partial positive charge at Ge versus B (+1.37 vs. +0.90 e); taken together with the relative unimportance of GeN π bonding (WBIs: GeN 0.44/0.46; BN: 0.93, 0.94), these data rationalize the uptake of IMe 4 at germanium, rather than boron in a molecule offering two Lewis acidic centers (i.e. 3‐Cl / 3‐N 3 ).