On the substitution-reaction of IF 5 by oxo-compounds

Abstract

Fluorine in IF 5 can be replaced by oxogroups using silylated alcoholes, carboxylates or siloxane itself. Systematic investigations of the fluorine-monoalcoholate-exchange in solution [1] show that IF 4(OR) is the only stable exchange-product at room temperature. Higher substitution products are unstable and undergo bismutation- and elimination-reactions: IF 3(OR) 2 → IF 4(OR) + IF 2(OR) 3 IF 2(OR) 3 ▪ IF 2O(OR) IO 2OR as the final product of nucleophilic exchange results on different routes: ▪ α-Branching in the aliphatic alcoholic group results in higher instability (alkylfluoride-elimination) of the iodine(V)fluoride alcoholates. No stable iodine(V)fluoride phenolates can be prepared. Using di- and trialcoholates two competing reaction products can be observed: IF 4O(CRR′) nOIF 4 and IF 3[O(CRR′) nO] In addition higher exchange products are formed: IF[O(CRR′)nO]2 Expanding our exchange-concept to the IF 5-carboxylate-system it was possible to synthesize IO(O 2C-R) 3, IO 2(O 2C-R), and in the case of the oxalate-group: IF 3(O 2CCO 2) and IFO(O 2CCO 2).