Abstract: | The versatile synthetic precursor methanolate‐bridged title rhodium complex, Rh2(CH3O)2(C12H6F4)2] or Rh(μ‐OCH3)(tfbb)]2 tfbb = tetrafluorobenzobarrelene or 3,4,5,6‐tetrafluorotricyclo6.2.2.02,7]dodeca‐2(7),3,5,9,11‐pentaene], has been structurally characterized. The asymmetric unit contains half a molecule that can be expanded via a twofold axis. The title compound has been shown to be a dinuclear rhodium complex where each metal centre is coordinated by two O atoms from two bridging methanolate groups and by the olefinic bonds of a tfbb ligand. Comparison of the bite angles of tfbb, norbornadiene (nbd) and cyclooctadiene (cod) olefins in their η4‐coordination to rhodium reveals similarities between the tfbb and nbd ligands, which are much more rigid than cod. The short distance found between the distorted square‐planar metal centres 2.8351 (4) Å] has been related to the syn conformation of the folded core `RhORhO' ring. |