A Modular Strategy for Expanding Electron-Sink Capacity in Noncanonical Cluster Assemblies

A modular synthetic strategy is described whereby organometallic complexes exhibiting considerable electron-sink capacity may be assembled by using only a few simple molecular components. The Fe₂(PPh₂)₂(CO)₅ fragment was selected as a common electroactive component and was assembled around aromatic cores bearing one, two, or three isocyanide functional groups, with the resultant complexes possessing electron-sink capacities of two, four, and six electrons, respectively. The latter complex is noteworthy in that its electron-sink capacity was found to rival that of large multinuclear clusters (e.g., [Ni₃₂C₆(CO)₃₆]^6- and [Ni₃₈Pt₆(CO)₄₈]^6-), which are often considered as benchmarks of electron-sink behavior. Moreover, the modular assembly bearing three Fe₂(PPh₂)₂(CO)₅ fragments was observed to undergo reduction to a hexaanionic state over a potential window of about -1.4 to -2.1 V (vs Fc/Fc⁺), the relatively compressed range being attributed to potential inversions operative during the addition of the second, fourth, and sixth electrons. Such complexes may be designated noncanonical clusters because they exhibit redox properties similar to those of large multinuclear clusters yet lack the extensive network of metal-metal bonds and the condensed metallic cores that typify the latter.