Heterometallic Cu2Fe and Zn2Fe2 Complexes Derived from [Fe(CO)4]2– and Cu/Fe Bifunctional N2O Activation Reactivity

The synthesis and characterization of two heterometallic clusters, [(IPr)Cu] 2 Fe(CO) 4 ( 1 ) and [(IPr)ZnFe(CO) 4 ] 2 ( 2 ), derived from Collman’s reagent are reported. Methylation of 1 with CH 3 I to produce (IPr)CuI and (IPr)CuFe(Me)(CO) 4 ( 3 ) was used to calibrate the relative reactivity of 1 to the previously studied analogue (IPr)Cu-FeCp(CO) 2 . Bifunctional N 2 O activation by 1 resulted in oxidation of a CO ligand to carbonate rather than the more typically observed CO 2, producing [(IPr)Cu] 2 (μ-CO 3 ) ( 4 ) stoichiometrically along with an iron byproduct that was trapped with PPh 3 as trans -Fe(CO) 3 (PPh 3 ) 2 .