Access to tetracyclic aromatics with bridgehead metals via metalla-click reactions

The never-ending pursuits for exploring aromatic molecular architectures result in the large libraries of aromatics with fascinating structures, which have greatly broadened the scope of aromaticity. Despite extensive efforts that have been paid to develop aromatic frameworks, the construction of polycyclic aromatics that share a bridgehead atom with more than three rings has never been accomplished.

Dinitrogen Activation by Tricoordinated Boron Species: A Systematic Design

Molecular nitrogen (N2), an abundant component of the atmosphere, is appealing for industrial value‐added products. However, its intrinsic inertness limits its activation to mainly metallic species. Environmental concerns and harsh reaction conditions have resulted in a demand for alternate nonmetallic and nontoxic routes to activate and functionalize N2 at ambient conditions. Comprehensive density functional theory (DFT) calculations are performed on N2 activation by boron species, specifically for the experimentally more accessible tricoordinated boron compounds.

Probing the Aromaticity and Stability of Metallatricycles by DFT Calculations: Toward Clar Structure in Organometallic Chemistry

Metallaaromatics have attracted considerable attention in recent years because they can display properties of both organic and organometallic species. However, it remains unclear whether Clar’s rule could be applied to organometallic chemistry despite its proposal in 1950s. Here, we investigate the relative stabilities of 49 organic and organometallic species by density functional theory (DFT) calculations.

Theoretical study on the stability and aromaticity in silapentafulvenes towards triplet ground state species

Pentafulvenes are dipolar hydrocarbons since they shift their π-electrons to achieve Hückel aromaticity and thus the electron donating groups at the exocyclic position can enhance their aromaticity. Silapentafulvenes are analogues of pentafulvene formed by the replacement of the carbon atoms at the exocyclic CC double bond with a silicon atom in pentafulvene. It remains unclear how the aromaticity of 5-silapentafulvenes and 6-silapentafulvenes can be changed due to the polarization of the CSi double bond.

Formation of Iridium(III) Complexes via Selective Activation of the C–H and N–H Bonds of a Dipyridylpyrrole Ligand

Treatment of [Ir(PPh3)3Cl] with 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine (Hdpp) in refluxing toluene affords an unexpected pyrrole-metalated iridium(III) hydride complex, [Ir(K2C,N-dpp)(H)(Cl)(PPh3)2] (1), via Cpyrrole–H activation, while the presence of the base KOtBu as the deprotonation reagent produces a pyridine-metalated iridium(III) hydride complex, [Ir(K3C,N,N-dpp)(H)(PPh3)2] (2), via Cpyridine–H activation.