Ir3Co6 and Co3Fe3 Dithiolene Cluster Complexes: Multiple Metal–Metal Bond Formation and Correlation between Structure and Internuclear Electronic Communication

π-Conjugated trinuclear iridium and cobalt dithiolenes undergo multiple metal–metal bond formation with Co2(CO)8 and Fe­(CO)5, giving rise to Ir3Co6 nonanuclear and Co3Fe3 hexanuclear cluster complexes 5 and 6, respectively. 5 retains a planar framework and intense π conjugation across the three iridadithiolenes and the phenylene bridge, which results in intense electronic communication among the three Co2(CO)5 units in reduced mixed-valent states.