From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications

Diarsene [L(MeO)GaAs]2 (L=HC[C(Me)N(Ar)]2, Ar=2,6-iPr2C6H3, 4) reacts with MeOTf and MeNHC (MeNHC=1,3,4,5-tetra-methylimidazol-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/+1, 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 & sdot;- (8 & sdot;-) and the NHC-coordinated radical cation [L(MeO)GaAsAs(MeNHC)Ga(OMe)L]& sdot;+ (9 & sdot;+), respectively, while the salt-elimination reaction of the triflate-coordinated diarsene 5 with Na[B(C6F5)4] gave [LGaAs]2[B(C6F5)4]2 (11) containing the dication [LGaAs]22+ (112+). Compounds 1-11 were characterized by 1H and 13C NMR, EPR (8, 9), IR, and UV-Vis spectroscopy and by single crystal X-ray diffraction (sc-XRD). DFT calculations provided a detailed understanding of the electronic nature of the diarsenes (4, 6) and the radical ions (8 & sdot;-, 9 & sdot;+), respectively. Stable main-group element-centered radicals have attracted tremendous attention. We report here the synthesis and molecular structures of both an arsenic-centered radical anion and a radical cation. In addition, the synthesis of base-coordinated and base-free diarsene dications is presented. image