The Arene‐Stabilized η5‐Pentamethylcyclopentadienyl Arsenic Dication [(η5‐Cp*)As(toluene)]2+

Double chloride abstraction of Cp*AsCl2 gives the dicationic arsenic species [(η5‐Cp*)As(tol)][B(C6F5)4]2 (2) (tol = toluene). This species is shown to exhibit Lewis super acidity by the Gutmann‐Beckett test and by fluoride abstraction from [NBu4][SbF6]. 2 participates in the FLP activation of THF affording [(η2‐Cp*)AsO(CH2)4(THF)][B(C6F5)4]2 (5). The reaction of 2 with PMe3 or dppe generates [(Me3P)2As][B(C6F5)4] (6) and [(σ‐Cp*)PMe3][B(C6F5)4] (7) or [(dppe)As][B(C6F5)4] (8) and [(dppe)(σ‐Cp*)2][B(C6F5)4]2 (9), respectively, via a facile cleavage of C‐As bonds, thus showcasing unusual reactivity of this unique As‐containing compound.

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