Synthesis, Spectroscopic Characterization, and Redox Reactivity of a Cyclic (Alkyl) Amino Carbene-Derived Arsamethine Cyanine Dye

Abstract

In our efforts to prepare a diarsenic allotrope supported by two cyclic alkyl amino carbene (CAAC) ligands we stumbled upon the synthesis of the first carbene-supported chloroarsinidene 3, which has been fully characterized by a combination of NMR spectroscopic and XRD methods. Although further reduction of 3 was not possible, we found that addition of a second equivalent of CAAC in refluxing toluene afforded the first example of a crystallographically characterized arsamethine cyanine dye (4). The arsenic(I) dye is structurally similar to phosphorus analogues, and contains an arsenide anion with two stereochemically active lone pairs supported by two iminium ligands. The UV/Visible spectrum and redox chemistry of 4 were also explored. Upon reduction with one equivalent of KC₈ , 3 is reduced to the originally targeted CAAC₂ As₂ allotrope 6, whereas oxidation provides access to the first example of an arsenic(II) radical dication (5).

Keywords: allotrope; arsenic; carbene; main group element; redox chemistry.