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The title molecules are sought in connection with various synthetic applications. The aliphatic fluorous alcohols R f   n  CH 2 OH (R f   n  = CF 3 (CF 2 )  n   -1 ; n = 11, 13, 15) are converted to the triflates R f   n  CH 2 OTf (Tf 2 O, pyridine; 22-61%) and then to R f   n  CH 2 I (NaI, acetone; 58-69%). Subsequent reactions with NaOCl/HCl give iodine(III) dichlorides R f   n  CH 2 ICl 2 ( n = 11, 13; 33-81%), which slowly evolve Cl 2 . The ethereal fluorous alcohols CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O)  x  CF(CF 3 )CH 2 OH ( 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, R f   n  I, are also inert, but additions of TMSCl to bis(trifluoroacetates) R f   n  I(OCOCF 3 ) 2 appear to generate R f   n  ICl 2 , which rapidly evolve Cl 2 . The aromatic fluorous iodides 1,3-R f6 C 6 H 4 I, 1,4-R f6 C 6 H 4 I, and 1,3-R f10 C 6 H 4 I are prepared from the corresponding diiodides, copper, and R f   n  I (110-130 °C, 50-60%), and afford quite stable R f   n  C 6 H 4 ICl 2 species upon reaction with NaOCl/HCl (80-89%). Iodinations of 1,3-(R f6 ) 2 C 6 H 4 and 1,3-(R f8 CH 2 CH 2 ) 2 C 6 H 4 (NIS or I 2 /H 5 IO 6 ) give 1,3,5-(R f6 ) 2 C 6 H 3 I and 1,2,4-(R f8 CH 2 CH 2 ) 2 C 6 H 3 I (77-93%). The former, the crystal structure of which is determined, reacts with Cl 2 to give a 75:25 ArICl 2 /ArI mixture, but partial Cl 2 evolution occurs upon work-up. The latter gives the easily isolated dichloride 1,2,4-(R f8 CH 2 CH 2 ) 2 C 6 H 3 ICl 2 (89%). The relative thermodynamic ease of dichlorination of these and other iodine(I) compounds is probed by DFT calculations.

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