Building upon the precedent of catalytically active (NHC)Cu-FeCp(CO)(2) complexes, a series of (NHC)Cu-[M] complexes were synthesized via the addition of Na+[M](-) reagents to (NHC)CuCl synthons. The different [M](-) anions used span a range of 7 x 10(7) relative nucleophilicity units, allowing for controlled variation of nucleophile/electrophile pairing in the heterobimetallic species. Direct Cu-M bonds (M = Cr, Mn, Co, Mo, Ru, W) formed readily when the bulky IPr carbene was used as a support. Crystallographic characterization and computational examination of these complexes was conducted. For the smaller IMes carbene, structural isomerism was observed when using the weakest [M](-) nucleophiles, with (IMes)Cu-[M] and {(IMes)(2)Cu}{Cu[M](2)} isomers being observed in equilibrium. Collectively, the series of complexes provides a toolbox for catalytic reaction discovery with precise control of structure-function relationships.