Diarsene [L(MeO)GaAs]2 (L = HC[C(Me)N(Ar)]2, Ar = 2,6iPr2C6H3, 4) reacts with MeOTf and MeNHC (MeNHC = 1,3,4,5‐tetramethylimidazol‐2‐ylidene) to the diarsene [L(TfO)GaAs]2 (5) and the carbene‐coordinated diarsene [L(MeO)GaAsAs(MeNHC)Ga(OMe)L] (6). The NHC‐coordination results in an inversion of the redox properties of the diarsene 4, which shows only a reversible reduction event at E1/2 = −2.06 V vs Fc0/+, whereas the carbene‐coordinated diarsene 6 shows a reversible oxidation event at E1/2 = −1.31 V vs Fc0/+1. Single electron transfer reactions of 4 and 6 yielded
[K[2.2.2.]cryp][L(MeO)GaAs]2 (8) and [L(MeO)GaAsAs(MeNHC)Ga(OMe)L][B(C6F5)4] (9) containing the radical anion [L(MeO)GaAs]2•−