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Nitrogen Atom Insertion into Ir−S and C−S Bonds Initiated by Photolysis of Iridium(III)−Azido-Dithiocarbamato Complexes

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journal contribution
posted on 12.08.2003, 00:00 by Takayoshi Suzuki, Antonio G. DiPasquale, James M. Mayer
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.