Bipyridine complexes of E(3+) (E = P, As, Sb, Bi): strong Lewis acids, sources of E(OTf)(3) and synthons for E(I) and E(V) cations

Triflate salts of trications [(bipy)(2)E](3+) ([6E][OTf](3)) and [(tbbipy)(2)E](3+) ([6′E][OTf](3)) (bipy = 2,2′-bipyridine, tbbipy = 4,4′-di-(t)butyl-2,2′-bipyridine; E = P, As, Sb, Bi) have been synthesized and comprehensively characterized. The unique molecular and electronic structures of this new class of complexes involving pnictogen Lewis acids has been assessed in the solid, solution and gas phases to reveal systematic variations in metric parameters, ligand lability and charge concentration. While the Lewis acidity of E(3+) has the trend E = Bi < Sb < As < P as determined by gas-phase calculations and (1)H NMR spectroscopy, the Lewis acidity of [6E](3+) has the trend E = P < As < Sb < Bi according to gas-phase calculations. Derivatives of [6′E][OTf](3) (E = P, As) are latent sources of E(OTf)(3) as demonstrated by their reactions with dmap, which give the corresponding derivatives of [(dmap)(3)E][OTf](3). The highly oxidizing nature of P(OTf)(3) and As(OTf)(3) is evidenced in reactions of [6′E][OTf](3) (E = P, As) with phosphines, which give E(I)-containing monocations [(R(3)P)(2)E](1+) and oxidatively coupled dications [R(3)PPR(3)](2+), illustrating new P–P and P–As bond forming strategies. Cations [6′E](3+) (E = P, As) are C–H bond activating agents that dehydrogenate 1,4-cyclohexadiene, with higher activity observed for E = P. Combinations of [6′E](3+) and (t)Bu(3)P activate H(2) and D(2) under mild conditions, evidencing frustrated Lewis pair activity. Oxidation of [6′P][OTf](3) with SO(2)Cl(2) gives [(tbbipy)(2)PCl(2)][OTf](3), containing a P(V)-trication, but there is no evidence of the analogous reaction with [6′As][OTf](3). The observations highlight new directions in the chemistry of highly charged cations and reveal a rich reactivity for p-block triflates E(OTf)(3), which can be accessed through derivatives of [6E][OTf](3) and [6′E][OTf](3).