Beschreibung:
<jats:title>Abstract</jats:title><jats:p>The paddlewheel‐shaped complex [Sb(<jats:italic>μ</jats:italic>‐pyS)<jats:sub>4</jats:sub>Rh]<jats:sub>2</jats:sub> (<jats:bold>1</jats:bold>) (pyS<jats:sup>−</jats:sup>= 2‐S‐C<jats:sub>5</jats:sub>H<jats:sub>4</jats:sub>N<jats:sup>−</jats:sup>) was synthesized from [Rh(pyS)(cod)]<jats:sub>2</jats:sub> (cod=1,5‐cyclooctadiene) and Sb(pyS)<jats:sub>3</jats:sub>. Upon oxidation with ONMe<jats:sub>3</jats:sub>, the complex [(<jats:italic>μ</jats:italic>‐O)Sb(<jats:italic>μ</jats:italic>‐pyS)<jats:sub>3</jats:sub>Rh(<jats:italic>κ</jats:italic><jats:sup>2</jats:sup>‐pyS)]<jats:sub>2</jats:sub> (<jats:bold>2</jats:bold>) is formed. Both <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> form dimers and feature short Rh−Sb bonds and bridging pyS ligands. <jats:sup>121</jats:sup>Sb Mössbauer spectro‐ scopy and computational studies were employed to elucidate the Rh−Sb bonding in <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold>. Both covalent (Rh−Sb, X‐type Sb ligand) and dative (Rh→Sb, Z‐type; Rh←Sb <jats:sc>L</jats:sc>‐type Sb ligand) interactions have to be considered for the description of their bonding situations.</jats:p>