Thionitrosyl‐ and Selenonitrosyliridium Complexes

The activation of elemental sulfur and selenium with electrophilic iridium nitride [Ir(N){N(CHCHPtBu2)2}]+ allowed the synthesis of thionitrosyl- and selenonitrosyliridium complexes. The crystallographic and spectroscopic characterization of this rare series of chalcogenonitrosyl complexes [Ir(NE){N(CHCHPtBu2)2}]+ (E = none, O, S, Se) is discussed in the context of bonding models. The experimental results indicate strong Ir-N-E multiple-bond character, in agreement with the previously proposed N-E donor-acceptor interaction as an appropriate description for the heavier chalcogens.