Heterolytic Cleavage of H(2) by Frustrated B/N Lewis Pairs

Treatment of the Lewis acid B(C(6)F(5))(3) with the Lewis base 2,6-dimethylpiperidine (DMP) resulted in the formation of the classical Lewis acid base adduct DMP-B(C(6)F(5))(3), la, which was anticipated to undergo thermal dissociation to the `'unquenched'' Lewis centers. The free Lewis pair was able to form a frustrated Lewis pair (FLP), which induced heterolytic splitting of H(2), affording the ionic product DMPH]HB(C(5)P(5))(3)], 1b. FLPs, derived from B(C(6)F(5))(3) and the bulky Lewis bases 2,2,6,6-tetramethylpiperidine (TMP) and 1,2,2,6,6-pentarnethylpiperidine (PMP), could also heterolytically activate H(2), affording the salts TMPH]HB(C(6)F(5))(3)], 2, and PMPH] HB(C(6)F(5))(3)], 3, respectively. In a VT NMR study the TMP/B(C(6)F(5))(3) reaction was studied in greater detail, trying to trace intermediates. The supposed most prominent intermediate, the TMP/H(2)/B(C(6)F(5))(3) complex, could, however, not be detected. The combination of B(C(6)F(5))(3) with the even more sterically demanding Lewis base 1-ethyl-2,2,6,6,-tetramethylpiperidine (Et-TMP) displayed FLP reactivity with H(2), but required the high temperature of 110 degrees C, forming 2,2,6,6-(CH(3))(4)C(5)H(6)NH(CH(2)CH(3))]HB(C(6)F(5))(3)], 4a. In the absence of H(2) the combination of B(C(6)F(5))(3) and Et-TMP generated at room temperature a mixture of 4a and 2,2,6,6-(CH(3))(4)C(5)H(6)N=CHCH(2)-B(C(6)F(5))(3)], 4b. 4b was formed via consecutive hydride and proton abstractions with Et-TMP as the base, generating 4a. 2,4,6-Tri-tert-butylpyridine (TTBP), exhibiting reduced Lewis basicity as compared to piperidine derivatives, showed FLP reactivity with B(C(6)F(5))(3), which gave in the presence of H(2) the TTBPH]HB(C(6)F(5))(3)], 5, salt as the only product after several hours. The steric demand of the Lewis bases was evaluated by aid of DFT calculations on borane adducts, which roughly correlated with the reaction temperature of H(2) splitting. 1a, 1b, 3, 4a, and 4b were studied by single-crystal X-ray diffraction analyses