Ligand-stabilized nanometer-sized gold particles are interesting building blocks for molecular electronics, precursors for catalysts, optical labels for biomolecules and diagnosis, and potential nontoxic carriers for therapeutics. In this work we characterize for the first time, by means of near-infrared and Raman spectroscopy and time-dependent density functional calculations, gold clusters protected with iron-carbonyl ligands, such as {Au(22)[Fe(CO)(4)](12)}(6-) shown in the figure. Surprisingly, our results show that these novel compounds bear many analogues to another, well-studied, class of gold clusters, namely those of thiolate-monolayer-protected gold clusters. Our work adds a new dimension to the rich chemistry of gold-based clusters that can be characterized as "molecular metals".