A series of clusters of the form [Et4N][Fe-2(CO)(6)(mu(3)-As)}(mu(3)-EFe(CO)(4))], where E is either P or As, were synthesized from [Et4N](2)[HAs{Fe(CO)(4)}(3)] and ECl3. AsCl3 gives the As-only compound; PCl3 produces compounds having two As atoms with one P atom, or one As atom and two P atoms, and they can exist as two possible isomers, one of which is chiral. The As2P and AsP2 clusters cocrystallize, and their structure as determined by single-crystal X-ray diffraction is given along with the structure of the As-only cluster. Analytical data as well as density functional theory calculations support the formation and geometries of the new molecules.