Single crystals for the oxygen-bridged iodonium triflates 1a and 1b as well as the nitrogen-bridged derivate 2a to verify their solid-state structures were obtained (Figure ). All structures show the typical, slightly distorted T-shaped structure which is commonly observed for I(III) derivates with a C-I-O angle close to 170° and a C-I-C angle close to 90°. An intramolecular interaction of the internal heteroatom to the iodine center could not be identified since the I-O distance is for all structures approximately 0.3 Å higher than to the corresponding external oxygen of the triflate.