Pentafluorophenylcompounds of polyvalent iodine

The oxidation of C₆F₅I by oxidizers containing positive chlorine was investigated with the intention to prepare pentafluorophenyliodine (III) compounds: C₆F₅IX₂, where X are halides or oxoderivatives. Using ClF, ClOCF₃, Cl₂/AlCl₃ or Cl₂O as oxidizers C₆F₅ IF₂, C₆F₅ I Cl₂ and C₆F₅I (OCl)₂ - all thermally unstable - could be prepared and characterized.In contrast to these compounds the perfluoroaromatic carboxylates: C₆F₅I O(O)C R_F]₂ are crystalline solids thermally stable up to 200 °C. Single crystal investigations show T-coordinated iodine with significant secondary bonding between iodine and the keto oxygens. C₆F₅ IO-formed by hydrolysis of C₆F₅IX₂ - changes if stored at RT forming (C₆F₅)₂I IO₃.(C₆F₅)₂I⁺ - formation is also observed when C₆F₅ IO is heated in inert (C₆F₅I, C₆H₆, CCl₄ …), protic (H₂O, CH₃OH, …) and strong acidic (FSO₃H …) dilution medium.C₆F₅IO reacts with acids, acid anhydrides and acid halides as could be shown by the preparation of C₆F₅ ICl₂ and C₆F₅ ICl (NO₃).Starting with C₆F₅ IX₂ different preparative ways for (C₆F₅)₂ I⁺ - compounds were successful. Principly (C₆F₅)₂ IX - compounds decompose thermally forming C₆F₅I + C₆F₅X.C₆F₅ IX₄ - compounds can be obtained from C₆F₅ IF₄ which is the specific displacement product of IF₅ with Si (C₆F₅)₄. By nucleophilic displacement it is possible to prepare C₆F₅ IF₂O, C₆F₅ IO₂, C₆F₅ IO (OAc_F)₂ and C₆F₅ I OC(CH₃)₂  C(CH₃)₂O]₂,wich are all white, thermally stable solids.For the fluorine-ligand-exchange we used silycompounds as reagents. If the ligand is oxidable by C₆F₅ I(V) a stepwise reduction via C₆F₅I(III) to C₆F₅I could be shown by NMR-measurements.