Synthesis, structure, and reactions of a copper–sulfido cluster comprised of the parent Cu2S unit: {(NHC)Cu}2(μ-S)† †Electronic supplementary information (ESI) available. CCDC 1421010–1421012. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03258j Click here for additional data file. Click here for additional data file.

The synthesis of the first Cu2(m-S) complex, {(IPr*)Cu}2(m-S) (IPr* 1⁄4 1,3-bis(2,6-(diphenylmethyl)-4methylphenyl)imidazol-2-ylidene; 1), has been accomplished via three synthetic routes: (1) salt metathesis between (IPr*)CuCl and Na2S; (2) silyl-deprotection reaction between (IPr*)Cu(SSiMe3) and (IPr*)CuF; and (3) acid–base reaction between (IPr*)Cu(SH) and (IPr*)Cu(OBu). The X-ray crystal structure of 1 exhibits two two-coordinate copper centers connected by a bent Cu–S–Cu linkage. Application of these synthetic routes to analogous precursors containing the sterically smaller ligand IPr (1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene), in place of IPr*, resulted in the formation of a transient product proposed as {(IPr)Cu}2(m-S) (2), which decomposes quickly in solution. The instability of 2 probably results from the insufficient steric protection provided by IPr ligands to the unsaturated Cu2(m-S) core; in contrast, 1 is stable both in solution and solid state for weeks. The nucleophilic sulfido ligand in 1 reacts with haloalkyl electrophiles (benzyl halides and dibromoalkanes) with formation of C–S bonds, affording (IPr*)Cu(SCH2Ph) and cyclic thioethers, respectively.