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

Takayoshi Suzuki; Antonio G DiPasquale; James M Mayer

doi:10.1021/ja0365779

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

J Am Chem Soc. 2003 Sep 3;125(35):10514-5. doi: 10.1021/ja0365779.

Authors

Takayoshi Suzuki¹, Antonio G DiPasquale, James M Mayer

Affiliation

¹ Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195-1700, USA. suzuki@chem.sci.osaka-u.ac.jp

PMID: 12940722
DOI: 10.1021/ja0365779

Abstract

Photolysis of acetonitrile solutions of Cp*Ir(R2dtc)(N3) [Cp* = eta5-C5Me5, R2dtc = S2CNR2; R = Me (1) or Et (1')] at temperatures below 0 degrees 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[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.