Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds: the role of iodine Lewis basicity

The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols RfnCH2OH (R-fn = CF3(CF2), 3, n = 11, 13, 15) are converted to the triflates RfnCH2OTf (Tf2O, pyridine; 22-61%) and then to RfnCH2I (NaI, acetone; 58-69%). Subsequent reactions with NaOCI/HCI give iodine(III) dichlorides RfnCH2ICl2 (n = 11, 13; 33-81%), which slowly evolve Cl-2. The ethereal fluorous alcohols CF3CF2CF2O(CF(CF3)CF2O),CF(CF3)CH2OH (x = 2-5) are similarly converted to triflates and then to iodides, but efforts to generate the corresponding dichlorides fail. Substrates lacking a methylene group, Rf,d, are also inert, but additions of TMSCI to bis(trifluoroacetates) Rf,d(OCOCF3)(2) appear to generate RfnICl2, which rapidly evolve Cl-2. The aromatic fluorous iodides 1,3-Rf6C6H4I, 1,4-Rf6C6H4I, and 1,3-Rf10C6H4I are prepared from the corresponding diiodides, copper, and RfnI (110-130 degrees C, 50-60%), and afford quite stable RfnC6H4ICl2\ species upon reaction with NaOCI/HCl (80-89%). Iodinations of 1,3-(R-f6)(2)C6H4 and 1,3-(Rf8CH2CH2)(2)C6H4 (NIS or I-2/H5IO6) give 1,3,5-(R-f6)(2)C6H3I and 1,2,4(Rf8CH2CH2)(2)C6H3I (77-93%). The former, the crystal structure of which is determined, reacts with Cl-2 to give a 75:25 ArICl2/ArI mixture, but partial Cl-2 evolution occurs upon work-up. The latter gives the easily isolated dichloride 1,2,4-(Rf8CH2CH2)(2)C6H3ICl2 (89%). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.