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

Photolysis of acetonitrile solutions of CpIr(R2dtc)(N3) [Cp = eta5-C5Me5, R2dtc = S2CNR2; R = Me (1) or Et (1')] at temperatures below 0 degrees C afford five-coordinate complexes CpIr{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, CpIr[SN=C(NMe2)S] (3), which could be crystallized as the corresponding dimer, {Cp*Ir[mu-SN=C(NMe2)S-kappa3S: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.