K⋅⋅⋅F/O Interactions Bridge Copper(I) Fluorinated Alkoxide Complexes and Facilitate Dioxygen Activation

Seven E[Cu(OR) 2 ] copper(I) complexes (E=K + , {K(18C6)} + (18C6=[18]crown‐6), or Ph 4 P + ; R=C 4 F 9 , CPhMe F 2 , and CMeMe F 2 ) have been prepared and their reactivity with O 2 studied. The K[Cu(OR) 2 ] species react with O 2 in a copper‐concentration‐dependent manner such that 2:1 and 3:1 Cu/O 2 adducts are observed manometrically at −78 °C. Analogous reactivity with O 2 is not observed with the {K(18C6)} + or Ph 4 P + derivatives. Solution conductivity data demonstrate that these K[Cu(OR) 2 ] complexes do not behave as 1:1 electrolytes in solution. The K + ions induce aggregation of multiple [Cu(OR) 2 ] − units through K⋅⋅⋅F/O interactions and thereby effect irreversible O 2 reduction by multiple Cu centers. Bond valence analyses for the potassium cations confirm the dominance of the fluorine interactions in the coordination spheres of K + ions. Intramolecular hydroxylation of ligand aryl and alkyl CH bonds is observed. Nucleophilic reactivity with CO 2 is observed for the oxygenated Cu complexes and a Cu II carbonate has been isolated and characterized.