The frustrated Lewis pair (FLP) comprised of B(C6F5)3 and 1,2,2,6,6-pentamethylpiperidine (PMP) can efficiently catalyze Z-selective hydrophosphonylation of terminal ynones with a Z/E selectivity of up to 20 : 1. Mechanistic studies suggest that the trans arrangement of the phosphite nucleophilic attack and hydrogen bond formation on the alkyne moiety is responsible for the observed Z-selectivity.

The frustrated Lewis pair (FLP) comprised of B(C6F5)3 and 1,2,2,6,6-pentamethylpiperidine (PMP) can efficiently catalyze Z-selective hydrophosphonylation of terminal ynones with a Z/E selectivity of up to 20 : 1. Mechanistic studies suggest that the trans arrangement of the phosphite nucleophilic attack and hydrogen bond formation on the alkyne moiety is responsible for the observed Z-selectivity.

2,6-Lutidine and its derivatives in the presence of B(C6F5)3 undergo tautomerization to yield the corresponding enamine·B(C6F5)3 adducts when catecholborane is applied as a precatalyst. This reaction provides a straightforward way for benzylic C–H borylation of lutidines.

Two 2,4,6-tris(trifluoromethyl)phenyl-substituted 2-(lutidinyl)organoboranes (5a and 5b) were prepared. These complexes can function as intramolecular vicinal B/N frustrated Lewis pairs to heterolytically activate dihydrogen. When these complexes were treated with HBpin, two different reaction pathways took place. Whereas the reaction between 5a and HBpin affords a formal ligand-redistribution product, the reaction of 5b with HBpin leads to a dearomative dehydroborylation product.

A bulky organoborane ArF2BMe (ArF = 2,4,6-tris(trifluoromethyl)phenyl, 1) has been synthesized. In C6D6 solution this organoborane and pyridine form a frustrated Lewis pair. Under mild conditions, 1 can efficiently catalyze 1,4-hydroboration of a series of pyridines. This reaction is highly chemo- and regioselective. The reaction intermediate, a boronium complex [Py2Bpin][ArF2B(H)Me] (3), was characterized in solution by NMR spectroscopy, which was also confirmed by DFT calculation.

The frustrated Lewis pair comprised of B(C6F5)3 and a boryl–borate lithium salt Li[pinBB(Ph)pin] can efficiently activate dihydrogen, pinacolborane and ethylene at ambient temperature. Theoretical studies suggest that the nucleophilic sp2 boryl moiety of Li[pinBB(Ph)pin] plays different roles in these reactions.

Frustrated Lewis pairs (FLPs) comprised of bis(2,4,6-tris(trifluoromethyl)phenyl)borane (1) and a secondary amine (such as HNiPr2 or HNEt2) readily react with CO2 at room temperature to afford ammonium carbamatoborate salts 2. When the reaction was carried out at 80 °C, carbamate boryl esters 3 were obtained with release of 1 equiv of H2. The iPr-substituted carbamate boryl ester 3a can function as an intramolecular FLP to activate H2, affording ammonium borylformate salt 4a and formamide adduct 5a. Two reaction pathways leading to the formation of 4a and 5a are proposed.

2,6-Lutidine and its derivatives in the presence of B(C6F5)3 undergo tautomerization to yield the corresponding enamine·B(C6F5)3 adducts when catecholborane is applied as a precatalyst. This reaction provides a straightforward way for benzylic C–H borylation of lutidines.

Two 2,4,6-tris(trifluoromethyl)phenyl-substituted 2-(lutidinyl)organoboranes (5a and 5b) were prepared. These complexes can function as intramolecular vicinal B/N frustrated Lewis pairs to heterolytically activate dihydrogen. When these complexes were treated with HBpin, two different reaction pathways took place. Whereas the reaction between 5a and HBpin affords a formal ligand-redistribution product, the reaction of 5b with HBpin leads to a dearomative dehydroborylation product.

The frustrated Lewis pair comprised of B(C6F5)3 and a boryl–borate lithium salt Li[pinBB(Ph)pin] can efficiently activate dihydrogen, pinacolborane and ethylene at ambient temperature. Theoretical studies suggest that the nucleophilic sp2 boryl moiety of Li[pinBB(Ph)pin] plays different roles in these reactions.