The bimetallic copper(I) complex Cu2L2 (cis-1) is formed with high diasteroselectivity from [Cu(NCCH3)(4)][BF4] and HL (4-tert-butyl phenyl(pyrrolato-2-yl-methylene)amine) in a kinetically controlled reaction. cis-1 features a rather short Cu center dot center dot center dot Cu distance of 2.4756(6) angstrom and is weakly emissive at room temperature in solution. Oxidatively, triggered disproportionation: of cis-1 yields elemental copper and the mononuclear copper(II) complex CuL2 (trans-2). Ode,electron reduction of trans-2 gives cuprate [2](-) with, a befit bis(pyrrolato) coordinated topper(I) entity. The imine donor atoms of [2](-) can insert an additional copper(I) ion giving exclusively the bimetallic complex cis-1 closing the oxidation-elimination-reduction-insertion cycle.