Description:
<jats:title>Abstract</jats:title><jats:p>The synthesis and characterization of two bimetallic, cationic low‐valent gallium–cryptand[2.2.2] complexes is reported. The reaction of cryptand[2.2.2] with Ga<jats:sub>2</jats:sub>Cl<jats:sub>4</jats:sub> gave two different cations, [Ga<jats:sub>3</jats:sub>Cl<jats:sub>4</jats:sub>(crypt‐222)]<jats:sup>+</jats:sup> (<jats:bold>1</jats:bold>) or [Ga<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>(crypt‐222)]<jats:sup>2+</jats:sup> (<jats:bold>2</jats:bold>), depending on whether or not trimethylsilyl triflate (Me<jats:sub>3</jats:sub>SiOTf) was added as a co‐reagent. Complexes <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> are the first examples of bimetallic cryptand[2.2.2] complexes, as well as the first low‐valent gallium–cryptand[2.2.2] complexes. Computational methods were used to evaluate the bonding in the gallium cores.</jats:p>