Abstract

Metal cations observed with tetrachloroaluminate anion provide insights into the structure and stability of reactive cations. Addition of tris(3,5-dimethylpyrazolyl)borate anion (TpMe2) to [BiCl2][AlCl4] traps a bismuth(III) dication, [TpMe2Bi]2+, possessing a highly electrophilic bismuth center with short coordinate Bi―N bonds. [TpMe2Bi]2+ has weak interactions with the chlorides of [Bi3Cl13]∞. Strong affinity of [TpMe2Bi]2+ with the triflate (OTf) observed in [TpMe2Bi(OTf)3]- demonstrates the high electrophilicity at bismuth.

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