Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals.

The construction of metal-carbon bonds is one of the most important issues of organometallic chemistry. However, the chelation of polydentate ligands to a metal via several metal-carbon bonds is rare. Metallapentalyne, which can be viewed as a 7-carbon (7C) chain coordinated to a metal via three metal-carbon bonds, was first reported in 2013. Although metallapentalyne contains a metal-carbon triple bond in a five-membered ring (5MR) and the bond angle around the carbyne carbon is only 129.5°, metallapentalyne exhibits excellent stability to air, moisture, and heat. Metallapentalyne possesses the rare planar Möbius aromaticity, which is in sharp contrast to the Hückel antiaromaticity in pentalyne. The metal fragment not only relieves the large ring strain present in pentalyne but also results in the transformation of the antiaromaticity in pentalyne to aromaticity in metallapentalyne. With the extension of the carbon chain from 7 to 12 carbon atoms, a series of novel polycyclic frameworks were constructed via the formation of several metal-carbon bonds. Some interesting phenomena were observed for these complexes. For instance, (1) the carbyne carbon of the 7C framework could react with both nucleophilic and electrophilic reagents, leading to the formation of 16- and 18-electron metallapentalenes; (2) σ aromaticity was first observed in an unsaturated system in the 8C framework; (3) two classical antiaromatic frameworks, cyclobutadiene and pentalene, were simultaneously stabilized in the 9C framework for the first time; (4) three fused 5MRs bridged by a metal are coplanar in the 10C framework; (5) the first [2 + 2 + 2] cycloaddition of a late transition metal carbyne complex with alkynes was realized during the construction of an 11C framework; (6) the largest number of carbon atoms coordinated to a metal atom in the equatorial plane was observed in the 12C framework; and (7) sharing of the transition metal by multiple aromatic units has seldom been observed in the metalla-aromatics. Therefore, the term carbolong chemistry has been used to describe the chemistry of these novel frameworks. More interestingly, carbolong complexes exhibit diverse properties, which could lead to potential future applications. As the discovery and creation of molecular fragments lead to advancements in chemistry, medical science, and materials chemistry, these novel polydentate carbon chain chelates might have important influences in these fields due to their facile synthesis, high stability, and unique properties.