Carbon ligands have long played an important role in organometallic chemistry. However, previous examples of all‐carbon chelating ligands are limited. Herein, we present a novel complex with an eleven‐atom carbon chain as a polydentate chelating ligand. This species was formed by the [2+2+2] cycloaddition reaction of two equivalents of an alkyne with an osmapentalyne that contains the smallest carbyne bond angle (127.9°) ever observed. Density functional calculations revealed that electron‐donating groups play a key role in the stabilization of this polydentate carbon‐chain chelate.

Isolation of the simplest 4π three‐membered heterocycles (1H‐azirine, oxirene, thiirene, and selenirene) remains a big challenge due to their π‐antiaromaticity and significant ring strain. Here we demonstrate that the incorporation of a transition‐metal fragment could stabilize the antiaromatic selenirene and pentalene frameworks simultaneously by density functional theory (DFT) calculations. Experimental verification leads to the Se‐containing metallapolycycles, osmapentaloselenirenes, with remarkable thermal stability.

Although the formation of metal–carbon σ bonds is a fundamental principle in organometallic chemistry, the direct bonding of one organic molecule with one metal center to generate more than two metal–carbon σ bonds remains a challenge. Herein, we report an aromaticity-driven method whereby multiyne chains are used to construct three metal–carbon σ bonds in a one-pot reaction under mild conditions. In this method, multiyne chains act as ligand precursors capable of chelating an osmium center to yield planar metallapolycycles, which exhibit aromaticity and good stability.

Polycyclic complexes containing a bridgehead transition metal are interesting species because the transition metal is shared by all the rings simultaneously. In this study, we present a novel osmium–bridgehead system with three fused five-membered rings. This novel framework can be viewed as a 10-atom carbon chain coordinating to the osmium center. In sharp contrast to the nonplanar organic analogue, this unique metallacycle exhibits good planarity, which was unambiguously verified by means of X-ray diffraction.

Metalla-aromatics are attractive species because they exhibit the properties of both organometallics and aromatics. Reported metal-bridged polycyclic aromatic complexes, as well as Möbius aromatic species, are still rare. Herein, we present the construction of two new metal-bridged polycyclic aromatic frameworks, α-metallapentalenofurans and lactone-fused metallapentalynes, by the reactions of osmapentalyne with terminal aryl alkynes in the presence of H2O or HBF4/H2O, respectively.

The synthesis of small cyclic metal carbynes is challenging due to the large angle strain associated with the highly distorted nonlinear triple bonds. Herein, we report a general route for the synthesis of five-membered cyclic metal carbyne complexes, osmapentalynes, by the reactions of an osmapentalene derivative with allene, alkyne, and alkene. Experimental observations and theoretical calculations document the aromaticity in the fused five-membered rings of osmapentalynes.

Antiaromatic species are substantially less thermodynamically stable than aromatic moieties. Herein, we report the stabilization of two classical antiaromatic frameworks, cyclobutadiene and pentalene, by introducing one metal fragment through the first [2+2] cycloaddition reaction of a late-transition-metal carbyne with alkynes. Experimental observations and theoretical calculations reveal that the metal fragment decreases the antiaromaticity in cyclobutadiene and pentalene simultaneously, leading to air- and moisture-stable products.

In general, aromaticity can be clarified as π- and σ-aromaticity according to the type of electrons with major contributions. The traditional π-aromaticity generally describes the π-conjugation in fully unsaturated rings whereas σ-aromaticity may stabilize fully saturated rings with delocalization caused by σ-electron conjugation. Reported herein is an example of σ-aromaticity in an unsaturated three-membered ring (3 MR), which is supported by experimental observations and theoretical calculations.

Aromaticity is one of the most important concepts in organic chemistry. A variety of metalla-aromatic compounds have been recently prepared and in most of those examples, the metal participates only in a monocyclic ring. In contrast, metal-bridged bicyclic aromatic molecules, in which a metal is shared between two aromatic rings, have been less developed. Herein, we report the first metal-bridged tricyclic aromatic system, in which the metal center is shared by three aromatic five-membered rings. These metalla-aromatics are formed by reaction between osmapentalyne and arene nucleophiles.

Highly stable five-membered metallacycloallenes were synthesized under mild conditions. Calculations revealed that the incorporation of transition-metal moieties relieves considerable strain and indicates a trend toward ring enlargement in the five-membered metallacycloallenes. Conversion into six-membered metallacycloallenes was confirmed experimentally.