Photolysis of THF solutions of 10-vertex [N(PPh3)2][6,6,6-(CO)3-closo-6,1-FeCB8H9] (1) in the presence of PEt3 results in [N(PPh3)2][6-CO-6,6-(PEt3)2-closo-6,1-FeCB8H9] (2), which readily oxidizes in air to form the neutral and paramagnetic, 17-electron Fe(III) species [6-CO-6,6-(PEt3)2-closo-6,1-FeCB8H9] (3). Substitution of one PEt3 ligand by cyanide occurs on addition of [NBun4][CN] and Me3NO to 3 in CH2Cl2, giving [NBun4][6-CO-6-CN-6-PEt3-closo-6,1-FeCB8H9] (4). When [IrCl(CO)(PPh3)2] and Tl[PF6] (1:1) are added to CH2Cl2 solutions of 4, the neutral, paramagnetic complex [6-{(μ-CN)Ir(CO)(PPh3)2}-6-CO-6-PEt3-closo-6,1-FeCB8H9] (5) is obtained. Results of X-ray diffraction studies carried out on 3 and 5 are presented herein.