Geometric Effects on C-C Coupling of Aryl-Carbenes under 2D Confinement.

It is well established that the confinement of reactants to two dimensions influences their reactivity. However, such confinement is often dominated by charge transfer effects between the reactants and the confining walls, in particular if the walls are conductive. Also, the reactivity of carbenes on metal surfaces is significantly affected by the charge transfer between the carbene and the metal, rendering the carbene more nucleophilic or electrophilic.

Elusive Arylalkylcarbenes in Solution and in Crystals: Facile 1,2-R (R = H, Ph) Migrations of 1,2,2-Triphenylethylidene.

Highly reactive arylalkylcarbenes generated in solution by photolysis of their aryldiazoalkane precursors tend to undergo competing inter- and intramolecular reactions to yield a complex mixture of products. Having previously shown the use of crystals to effectively control the reactivity of arylalkylcarbenes to afford high yields of a single product, it was of interest to investigate whether the crystalline environment could also enable spectroscopic detection of these intermediates en route to the photoproduct. Using 1,2,2-triphenyldiazoethane () as a model substrate to probe the effect of alternative reaction trajectories that yield triphenylethylene () by competing 1,2-H shift or 1,2-Ph migration, we report selectivities consistent with reaction from a spin-equilibrated carbene in solution, while reactions in crystals primarily afford alkene via a lattice-controlled 1,2-H shift.

Vibrational Circular Dichroism of a Chiral Triplet Nitrene Investigated Under Matrix-Isolation Conditions in Parahydrogen.

Vibrational circular dichroism (VCD) spectra of chiral high-spin organic radicals are expected to show a strong intensity enhancement and are thought to be difficult to predict using state-of-the-art theoretical methods. Herein we show that the chiral triplet nitrene obtained from photochemical cleavage of N from enantiopure 2-azido-9H-fluorenol does not feature extraordinarily strong intensities and that the experimental spectra match nicely with calculated ones. Thereby, this study demonstrates the general feasibility of studies on chiral high-spin organics by matrix-isolation VCD.

Chirality control of a single carbene molecule by tip-induced van der Waals interactions.

Non-covalent interactions such as van der Waals interactions and hydrogen bonds are crucial for the chiral induction and control of molecules, but it remains difficult to study them at the single-molecule level. Here, we report a carbene molecule on a copper surface as a prototype of an anchored molecule with a facile chirality change. We examine the influence of the attractive van der Waals interactions on the chirality change by regulating the tip-molecule distance, resulting in an excess of a carbene enantiomer.

Isomer-Specific Heavy-Atom Tunneling in the Ring Expansion of Fluorenylazirines.

The photolysis of 2-azidofluorene in solid argon at 3 K results in the formation of 2-fluorenylnitrene. The nitrene undergoes subsequent rearrangements to two isomeric didehydroazepines (ketenimines) which differ in the position of the N atom in the seven-membered ring. The rearrangement of the nitrene to the didehydroazepines proceeds in a two-step process.