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

Abstract

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 GaI/InI precursors by substitution chemistry, and display nucleophilic reactivity which is strongly influenced by the presence (or otherwise) of the K+ counterion.