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We report the syntheses of two rigid mesoionic carbene (MIC) ligands with a carbazole backbone via an intramolecular Finkelstein-Cyclisation cascade and investigate their coordination behavior towards nickel(II) acetate. Despite the...

A frustrated Lewis pair-catalyzed hydroboration of aromatic and aliphatic nitriles was developed. The catalyst provides the primary amines in high yields of 77-99% with catalyst loading as low as 2 mol%. The reaction displays high functional group tolerance towards esters, amides, nitro groups and aliphatic halides. The addition of the diborylated amines to ethyl 3phenylpropiolate proceeds with Z-selectivity with d.r. of > 99:1 in 77-90% yield over two steps. The reaction mechanism was investigated by control and computational experiments.

An isostructural series of boron/phosphorus Lewis pairs was systematically investigated. The association constants of the Lewis pairs were determined at variable temperatures, enabling the extraction of thermodynamic parameters. The stabilization of the Lewis adduct increased with increasing size of the dispersion energy donor groups, although the donor and acceptor properties of the Lewis pairs remained largely unchanged. This data was utilized to challenge state‐of‐the‐art quantum chemical methods, which finally led to an enhanced workflow for the determination of thermochemical properties of weakly bound Lewis pairs within an accuracy of 0.6 to 1.0 kcal mol−1 for computed association free energies.

Abbildung 3. EPR-Spektren der in TCE gelçsten Radikale bei 50 K, welche auf einem 180-GHz-EPR-Spektrometer gemessen wurden.Abbildung 4. Feldprofil für die verwendeten Radikale, die bei 100 K in TCE (90D:10 H)-Matrix unter 8-kHz-MAS gemessen wurden. Details zur Probenvorbereitung sind in der SI zu finden.Abbildung 5. Normierte 1 H-DNP-Verstärkung als Funktion der MW-Leistung für verschiedene Komponenten des Feldprofils: für BDPA (links) und 1-4-Amin (rechts). Die Daten für 1-3-Amin sind in Abbildung S2 in der SI dargestellt.