Nitrogen atom insertion into IR - S and C - S bonds initiated by photolysis of iridium(III) - azido-dithiocarbamato complexes

Photolysis of acetonitrile solutions of Cp*Ir(R₂dtc)(N₃) [Cp* = η⁵-C₅Me₅, R₂dtc = S₂CNR₂; R = Me (1) or Et (1′)] at temperatures below 0 °C afford five-coordinate complexes Cp*Ir{NSC(NR₂)S} (2 or 2′), where a nitrogen atom has been inserted into one of the Ir-S bonds. In solution, complex 2 thermally convert to the azaethene-1,2-dithiolate complex, Cp*Ir[SN=C(NMe₂)S] (3), which could be crystallized as the corresponding dimer, {Cp*Ir[μ-SN=C(NMe₂)S-κ³S:S,S′]}2 (4). As a result, a nitrogen atom that originated in the azide ligand is transferred into a C-S bond of the dithiocarbamate.