A Bridged Copper(I) Diiodine Complex

The bridged copper diiodine complex [( μ ‐I ₂ ){Cu[Al(OR ^F ) ₄ ]} ₂ ] ( 1 ) was obtained by simple ligand substitution of the dinitrogen ligand in [(N ₂ )Cu{Al(OR ^F ) ₄ }] by I ₂ . In 1 , the two independent π *‐MOs of the I ₂ ligand act as donors towards the Lewis acidic Cu[Al(OR ^F ) ₄ ] fragments, which is reflected by its bent staggered coordination mode in the solid state as determined by single crystal X‐ray diffraction. Cu─I bonds in 1 are exceptionally short, and the I─I bond is elongated compared to the analogous silver compound, while AIM analysis indicates a significant amount of positive charge localized on the iodine atoms. Consequently, 1 is structurally already close to a molecular ‘CuI’ and displays pronounced oxidizing power with loss of the I─I bond, inducing at room temperature the rapid formation of solid CuI by oxidative decomposition of solvents such as n ‐pentane and also the [Al(OR ^F ) ₄ ] ⁻ counterion.