Synthesis, Isolation, and Reactivity Studies of ‘Naked’ Acyclic Gallyl and Indyl Anions

By exploiting the electronic capabilities of the N‐heterocyclic boryloxy (NHBO) ligand, we have synthesized “naked” acyclic gallyl [Ga{OB(NDippCH) 2 } 2 ] − and indyl [In{OB(NDippCH) 2 } 2 ] − anions (as their [K(2.2.2‐crypt)] + salts) through K + abstraction from [KGa{OB(NDippCH) 2 } 2 ] and [KIn{OB(NDippCH) 2 } 2 ] using 2.2.2‐crypt. These systems represent the first O‐ligated gallyl/indyl systems, are ultimately accessed from cyclopentadienyl Ga I /In I precursors by substitution chemistry, and display nucleophilic reactivity which is strongly influenced by the presence (or otherwise) of the K + counterion.