Organometallic chemistry

Carbyne anions are under explored and poorly understood, owing to their isolation being unknown. Now, the synthesis and isolation of copper phosphinocarbyne anion complexes are reported. Displaying the reactivity of a carbyne anion, these complexes provide access to singlet carbenes, alkenes and ethenimines.

Introducing unknown compound classes is the key to extent the chemical space qualitatively. Here the authors report on a concept to design heterocyclic compound classes rationally and the synthesis of unknown classes of N-heterocyclic compounds

Stereodefined 1,2-dimetallated alkenes are underexplored in organic synthesis due to their relatively low stability. Now, the reductive anti-1,2-dimetallation of alkynes provides access to trans-1,2-dimagnesio- and 1,2-dialuminoalkenes. The process uses sodium dispersion as a reducing agent with organomagnesium and organoaluminium halides as reduction-resistant electrophiles.

Aromaticity is a ubiquitous concept in organic chemistry yet it is less widespread for inorganic species. Now the cluster [(CpRu)₃Bi₆]^–, obtained as part of a soluble salt, has been shown to exhibit aromatic behaviour referred to as φ-type, owing to a highly regular {Bi₆} substructure causing a non-localizable molecular orbital of \(f_{z^3}\)-like symmetry.

Reactions induced by σ-aromaticity are uncommon compared with those induced by π-aromaticity. Now, a π- and σ-aromaticity relay strategy is developed to realize the ring contraction of metallacyclobutadiene to metallacyclopropene. This reaction involves the release of π-antiaromaticity to afford a π-aromatic intermediate, followed by ring reclosure to form σ-aromatic metallacyclopropene.

Converting low-cost inorganic chemicals into value-added organic chemicals is a longstanding goal in chemistry. Here the authors describe a silver-catalysed chemoselective carbene N−H insertion reaction, providing access to primary amines from aqueous ammonia and diazo compounds.