α-CH acidity of alkyl–B(C(6)F(5))(2) compounds – the role of stabilized borata-alkene formation in frustrated Lewis pair chemistry

Alkyl–B(C(6)F(5))(2) boranes are markedly α-CH-acidic. Using DFT we have calculated the pK (a)-values of a series of examples. Typically, (C(6)F(5))(2)B–CH(3) [pK (a) (calcd) = 18.3 in DMSO, 16.2 in dichloromethane] is almost as CH-acidic as cyclopentadiene. However, this α-CH–B(C(6)F(5))(2) acidity is in most cases not sufficient to allow for internal proton transfer in vicinal phosphane/borane frustrated Lewis pairs (FLPs). An exception is the slightly endergonic (+0.3 kcal mol(–1)) tautomerization of the in situ generated indane derived 1,3-P/B FLP 6 to its zwitterionic borata-alkene/phosphonium isomer 7, which was successfully trapped by Piers' borane [HB(C(6)F(5))(2)] to yield the stable product 8. The pronounced α-CH[B] carbanion stabilization can be used synthetically. We have found that the dienyl borane E-H(2)C[double bond, length as m-dash]C(Me)CH[double bond, length as m-dash]CHB(C(6)F(5))(2) undergoes clean, thermally induced 1,4-hydrophosphination reactions with HPR(2) (R: phenyl, mesityl, or t-butyl) reagents. α-CHB(C(6)F(5))(2) carbanion (i.e. borata-alkene) stabilization in the respective intermediates probably plays a decisive role in these reactions.