Abstract
A square‐planar coordination geometry was found for the complex [Ir(cod){(−)‐norphos}][PF~6~] (1b[PF~6~]; cod = cylcoocta‐1,5‐diene and (−)‐norphos = [(2__R__,3__R__)‐8‐9‐10‐trinorborn‐5‐ene‐2,3‐diyl]bis(diphenylphosphine)) in the solid state by X‐ray diffraction. Crystal data: monoclinic, space group P__2~1~, a = 10.751 (6), b = 18.669(14), c = 12.037(8) Å, β = 114.82(5)°, Z = 2. A total structural assignment including the configurational and conformational aspects of this and the related compounds [Ir(bishosphine)(cod)]X (bisphosphine = (−)‐chiraphos = (2__S,3__S__)‐2,3‐bis(diphenylphosphino)butane and (−)‐norphos, X = Cl, CF~3~SO~3~, or PF~6~) was carried out in solution by one‐ and two‐dimensional NMR spectroscopy. The complexes containing the CF~3~SO~3~^−^ and PF~6~^−^ anions are four‐coordinate cations with square‐planar geometry, whereas the chlorides are five‐coordinate neutral compounds showing solvent‐dependent dynamic behaviour. In toluene, two diastereoisomers of [IrCl(cod){(−)‐norphos}] (2b) exist and interconvert slowly at room temperature. This interchange is fast in CDCl~3~ solution, and it is likely to involve Cl dissociation and the formation of the cation [Ir(cod){(−)‐norphos}]^+^ as an intermediate.