The possibility of obtaining frustrated Lewis pairs (FLPs) suitable for H2-activation based on the Lewis acid B(Ohfip)3 1 (Ohfip = OC(H)(CF3)2) was investigated. In this context, the crystal structure of 1 as well as the crystal structure of the very weak adduct 1·NCMe was determined. When reacting solutions of 1 with H2 (1 bar) and selected phosphanes, amines, pyridines and N-heterocyclic carbenes, dihydrogen activation was never observed. Without H2, adduct formation with 1 was observed to be an equilibrium process, regardless of the Lewis base adduct. Thus, the thermodynamics of H2 activation of 1 in comparison with the well-known B(C6F5)3 was analyzed using DFT calculations in the gas phase and different solvents (CH2Cl2, ortho-difluorobenzene and acetonitrile). These investigations indicated that FLP chemistry based on 1 is considerably less favored than that with B(C6F5)3. This is in agreement with control NMR experiments indicating hydride transfer from [H-B(Ohfip)3](-) upon reaction with B(C6F5)3, giving [H-B(C6F5)3](-) and B(Ohfip)3 in toluene and also MeCN. Induced by these unsuccessful reactions, the Lewis acidity towards HSAB hard and soft ions was investigated for gaining a deeper insight. A unified reference system based on the trimethylsilyl compounds Me3Si-Y (Y = F, Cl, H, Me) and their respective ions Me3Si(+)/Y(-) calculated at the G3 level was chosen as the anchor point. The individual ion affinities were then assessed based on subsequent isodesmic reactions calculated at a much less expensive level (RI-)BP86/SV(P). This method was validated by systematic calculations of smaller reference systems at the frozen core CCSD(T) level with correlation effects extrapolated to a full quadruple-ζ basis. Overall, 33 common and frequently used Lewis acids were ranked with respect to their FIA, CIA, HIA and MIA (fluoride/chloride/hydride/methyl ion affinity).

We report herein the synthesis and full characterization of the donor-free Lewis superacids Al(OR(F))(3) with OR(F) = OC(CF(3))(3) (1) and OC(C(5)F(10))C(6)F(5) (2), the stabilization of 1 as adducts with the very weak Lewis bases PhF, 1,2-F(2)C(6)H(4), and SO(2), as well as the internal C-F activation pathway of 1 leading to Al(2)(F)(OR(F))(5) (4) and trimeric [FAl(OR(F))(2)](3) (5, OR(F) = OC(CF(3))(3)). Insights have been gained from NMR studies, single-crystal structure determinations, and DFT calculations. The usefulness of these Lewis acids for halide abstractions has been demonstrated by reactions with trityl chloride (NMR; crystal structures). The trityl salts allow the introduction of new, heteroleptic weakly coordinating [Cl-Al(OR(F))(3)](-) anions, for example, by hydride or alkyl abstraction reactions.

Abstract:The ferrocenylboranes (BOhfip 2 )Fc and 1