Paddlewheel complexes with Ir-2(5+) cores and having an unpaired electron have been made for the first time. These have been prepared by reacting (COD)Ir-I(DArF)(2)Ir-III(CF3CO2)(2)(H2O) with two molar equivalents of HDArF (DArF = N,N'-diarylformamidinate, Ar = p-anisyl and p-chlorophenyl, and COD = 1,5-cyclooctadiene). In the presence of CH2Cl2, the corresponding Ir-2(mu-DArF)(4)(eta(1)-O2CCF3). 2CH(2)Cl(2) compounds are isolated in ca. 50% yield. The metal-metal distances are 2.5073(9) and 2.513(1) Angstrom for the p-anisyl and p-chlorophenyl derivatives, respectively. We also report the structure of the dinuclear compound [Ir-2(cis-mu-DAniF)(2)(MeCN)(6)] (BF4)(2). 2CH(3)-CN, which has an Ir-Ir bond distance of 2.6019(4) Angstrom, and that of a starting material, [Ir(DAniF)(COD)](2). toluene.