Beschreibung:
<jats:p>Herein we report on the facile access to a Ga<jats:sup>I</jats:sup> and In<jats:sup>I</jats:sup> complex salt of pentamethyldiethylenetriamine (PMDTA) with the weakly coordinating counterion [Al(OR<jats:sup>F</jats:sup>)<jats:sub>4</jats:sub>]<jats:sup>–</jats:sup> [R<jats:sup>F</jats:sup> = C(CF<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>]. Thus, the low temperature reaction of [M(PhF)<jats:sub>2</jats:sub>]<jats:sup>+</jats:sup> (M = Ga, In) solutions in 1,2‐F<jats:sub>2</jats:sub>C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub> (<jats:italic>o</jats:italic>DFB) with PMDTA yielded the title compounds M(PMDTA)<jats:sup>+</jats:sup>[Al(OR<jats:sup>F</jats:sup>)<jats:sub>4</jats:sub>]<jats:sup>–</jats:sup> (M = Ga <jats:bold>1</jats:bold>, in <jats:bold>2</jats:bold>) in non‐optimized yields. Both compounds are highly sensitive towards air and moisture, have a rather limited lifetime at room temperature, but were structurally characterized.</jats:p>