Beschreibung:
<jats:title>Abstract</jats:title><jats:p>A novel sterically demanding bis(4‐benzhydryl‐benzoxazol‐2‐yl)methane ligand <jats:bold>6</jats:bold> (<jats:sup>4−BzhH2</jats:sup>BoxCH<jats:sub>2</jats:sub>) was gained in a straightforward six‐step synthesis. Starting from this ligand monomeric [<jats:italic>M</jats:italic>(<jats:sup>4‐BzhH2</jats:sup>BoxCH)] (<jats:italic>M</jats:italic>=Na (<jats:bold>7</jats:bold>), K (<jats:bold>8<jats:sub>1</jats:sub></jats:bold>)) and dimeric [{<jats:italic>M</jats:italic>(<jats:sup>4‐BzhH2</jats:sup>BoxCH)}<jats:sub>2</jats:sub>] (<jats:italic>M</jats:italic>=K (<jats:bold>8<jats:sub>2</jats:sub></jats:bold>), Rb (<jats:bold>9</jats:bold>), Cs (<jats:bold>10</jats:bold>)) alkali metal complexes were synthesised by deprotonation. Abstraction of the potassium ion of <jats:bold>8</jats:bold> by reaction with 18‐crown‐6 resulted in the solvent separated ion pair [{(THF)<jats:sub>2</jats:sub>K@(18‐crown‐6)}{bis(4‐benzhydryl‐benzoxazol‐2‐yl)methanide}] (<jats:bold>11</jats:bold>), including the energetically favoured monoanionic (<jats:italic>E</jats:italic>,<jats:italic>E</jats:italic>)‐(<jats:sup>4‐BzhH2</jats:sup>BoxCH) ligand. Further reaction of <jats:sup>4−BzhH2</jats:sup>BoxCH<jats:sub>2</jats:sub> with three equivalents KH and two equivalents 18‐crown‐6 yielded polymeric [{(THF)<jats:sub>2</jats:sub>K@(18‐crown‐6)}{K@(18‐crown‐6)K(<jats:sup>4‐Bzh</jats:sup>BoxCH)}]<jats:sub><jats:italic>n</jats:italic></jats:sub> (<jats:italic>n</jats:italic>→∞) (<jats:bold>12</jats:bold>) containing a trianionic ligand. The neutral ligand and herein reported alkali complexes were characterised by single X‐ray analyses identifying the latter as a promising precursor for low‐valent main group complexes.</jats:p>