Boryl Ancillary Ligands: Influencing Stability and Reactivity of Amidinato‐Silanone and Germanone Systems in Ammonia Activation

While the nucleophilic addition of ammonia to ketones is an archetypal reaction in classical organic chemistry, the reactivity of heavier group 14 carbonyl analogues (R2E=O; E = Si, Ge, Sn, or Pb) with NH3 remains sparsely investigated, primarily due to the synthetic difficulties in accessing heavier ketone congeners. Herein, we present a room‐temperature stable boryl‐substituted amidinato‐silanone {(HCDippN)2B}{PhC(tBuN)2}Si=O (Dipp = 2,6‐iPr2C6H3) (together with its germanone analogue), formed from the corresponding silylene under a N2O atmosphere. This system reacts cleanly with ammonia in 1,2‐fashion to give an isolable sila‐hemiaminal complex {(HCDippN)2B}{PhC(tBuN)2}Si(OH)(NH2). Quantum chemical cal‐culations reveal that the formation of this sila‐hemiaminal is crucially dependent on the nature of the ancillary ligand scaffold. It is facilitated thermodynamically by the hemi‐lability of the amidinate ligand (which allows for the formation of an energetically critical intramolecular N…HO hydrogen bond within the product) and is enabled mechanistically by a process in which the silanone initially acts in umpolung fashion as a base (rather than an acid), due to the strongly electron‐releasing and sterically bulky nature of the ancillary boryl ligand.