The versatile PNPtBu scaffold acts as a noninnocent, pseudobridging ligand toward CuX (ratio 1:2), resulting in a 1D-coordination chain. Ligand dearomatization by using base and subsequent addition of thiols leads to the unique, asymmetrically substituted, dinuclear Cu species with reactive Br coligands and the versatile PNPtBu ligand that bridges the two Cu centers (see scheme).