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Compound Ph3As(OTf)2 as a pentacoordinated AsV Lewis acid readily forms dicationic Lewis acid/base adducts upon addition of various Lewis bases. It also represents a stronger chloride‐abstracting agent than Me3SiOTf and facilitates the reductive coupling of PCl3 in the presence of AsPh3 to the unprecedented cation [P7(AsPh3)3]3+ as triflate salt. This crystallographically characterized nortricyclane‐type...
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