Statistical models for the prediction of the energy profile of H2 activation by silylenes and germylenes were developed. A simple model based on increments of the elements in α-position enabled robus...

The pyridylketene has previously been isolated via matrix isolation and demonstrated potential in the synthesis of N-heterocycles. Herein, we report the synthesis and isolation of the pyridylketenyl anion through conventional synthetic methods, involving metalation and subsequent carbonylation of the readily available 2-pyridyl ylide. Quantum chemical calculations reveal extensive delocalization of the negative charge across the entire molecular framework, resulting in multiple nucleophilic sites that are best described by a series of resonance structures. IR spectroscopic and X-ray diffraction data corroborate this electronic structure, indicating a markedly compressed C–C–C–O moiety. The pronounced charge delocalization enables diverse reactivities and promotes cyclization pathways involving the pyridine nitrogen. Accordingly, the pyridylketenyl anion serves as a versatile precursor for the construction of heterocycles featuring triazolone, quinolizine, and indolizine motifs, underscoring its broad applicability as a building block in heterocycle synthesis.

N-heterocyclic carbenes (NHCs) function as “molecular scissors,” cleaving otherwise inert Sb═Sb bonds in distibenes to generate monomeric, zwitterionic stibinide species. These intermediates act as e...

Synthesis and Reactivity of Heavy Azadipnictiridines

Low-valent cadmium compounds have remained largely unexplored as electron reservoirs, with no precedent for their use in reduction or bond activation chemistry. Here, we address this gap by integratin...

Small organic rings are important molecular entities that have long played a crucial role in organic synthesis and medicinal chemistry. Similarly, small inorganic rings have shown promise in promoting...