| Summary: | In order to investigate the coordination chemistry of <i>O</i>-alkyl <i>N</i>-aryl thiocarbamate ligands toward coinage metals, CuBr was reacted with one equivalent of MeOC(=S)N(H)Ph <b>L</b> in MeCN solution to afford the 1D-polymeric title compound [{Cu(<i>μ</i><sub>2</sub>-Br)<sub>2</sub>Cu}{μ<sub>2</sub>-MeOC(=S)N(H)Ph}<sub>2</sub>]<i><sub>n</sub></i> <b>CP1</b>. Compound <b>1</b> was characterized by IR spectroscopy and an elemental analysis. The formation of a polymeric 1D ribbon built upon μ<sub>2</sub>-bridging bromido and thione ligands via the C=S bond was ascertained by a single-crystal X-ray diffraction study performed at 100 K. In the presence of PAr<sub>3</sub> (Ar = Ph, <i>p</i>-Tol), the polymer chain was broken to yield the mononuclear complexes [(Ar<sub>3</sub>P)<sub>2</sub>Cu{MeOC(=S)N(H)Ph}Br] <b>C1</b> and <b>C2</b>.
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