Frustrated Lewis pairs (FLPs) have a great potential for activation of small molecules. Most known FLP systems are based on boron or aluminum atoms as acid functions, few on zinc, and only two on boron-isoelectronic silicenium cation systems. The first FLP system based on a neutral silane, (C2F5)3SiCH2P(tBu)2 (1), was prepared from (C2F5)3SiCl with C2F5 groups of very high electronegativity and LiCH2P(tBu)2. 1 is capable of cleaving hydrogen, and adds CO2 and SO2. Hydrogen splitting was confirmed by H/D scrambling reactions. The structures of 1, its CO2 and SO2 adducts, and a decomposition product with CO2 were elucidated by X-ray diffraction.
Tris[tetrafluoro-4-(trifluoromethyl)phenyl]borane (BTolF) was prepared by treating boron tribromide with tetrameric F 3 CC 6 F 4 -Cu I .The F 3 CC 6 F 4 -Cu I was generated from F 3 CC 6 F 4 MgBr and copper(I) bromide.L ewis acidities of BTolF evaluated by the Gutmann-Beckett method and calculated fluoride-ion affinities are 9and 10 %, respectively,higher than that of tris(pentafluorophenyl)borane (BCF) and even higher than that of SbF 5 .T he molecular structures of BTolF and BCF were determined by gas-phase electron diffraction, that of BTolF also by single-crystal X-ray diffraction.
The doubly Lewis-acid functionalised aniline PhN[(CH2)3B(C6F5)2]2 features two competing boron functions in fast exchange for binding to the central Lewis base. It shows catalytic activity typical for FLPs in H/D-scrambling and catalytic hydrogenation experiments. By contrast, the singly acid-functionalised PhMeN(CH2)3B(C6F5)2 reveals a dramatically smaller catalytic activity in analogous experiments.
Deprotonation of the methylpyridines 2,6-lutidine, 2-picoline, 4-dimethylamino-2,6-dimethylpyridine as well as 2,6-dimethyl-4-(piperidine-1-yl)pyridine with n-butyllithium or n-butyllithium/KO-t-Bu at the methyl positions led to the corresponding organolithium or -potassium compounds. Treatment with ClB(C6F5)2 resulted in formation of the 2-borylmethylpyridines py-CH2-B(C6F5)2. They are monomeric and form intramolecular B-N bonds and four-membered rings. A short intramolecular B-N distance was observed in the crystal structure of the dimethylamino-functionalized derivative and proposed to be responsible for the low reactivity of the products towards hydrogen, thf, acetonitrile and CO2. Hydroboration of 6-tert-butyl-2-but-4'-enylpyridine with HB(C6F5)2 led to the corresponding hydroboration product t-Bu-py-(CH2)4-B(C6F5)2 which shows no intramolecular B-N bond formation due to steric crowding. H/D-scrambling experiments with a H2/D2 mixture revealed its reactivity towards hydrogen.
The structures of the three para‐substituted halotetrafluoropyridines with chlorine, bromine, and iodine have been determined in the solid state (X‐ray diffraction). The structures of these compounds and that of pentafluoropyridine were also determined in the gas phase (electron diffraction). Structures in the solid state of the bromine and iodine derivatives exhibit halogen bonding as a structure‐determining motif. On the way to an investigation of halogen bond formation of halotetrafluoropyridines in the solid state with the stronger Lewis base pyridine, co‐crystals of benzene adducts were investigated to gain an understanding of the influence of aryl–aryl interactions. These co‐crystals showed halogen bonding only for the two heavier halotetrafluoropyridines. In the pyridine co‐crystals halogen bonding was observed for all three para‐halotetrafluoropyridines. The formation of homodimers and heterodimers with pyridine is also supported by quantum‐chemical calculations of electron density topologies and natural bond orbitals.
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