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The activation of CH bonds in arenes and heteroarenes has attracted considerable attention in recent years. Examples of the activation of two or more CH bonds in arenes or heteroarenes are rare. In recent studies it has been found that certain polynuclear metal carbonyl complexes, such as Re 2 (CO) 8 (μ-C 6 H 5 )(μ-H), 1 and Os 3 (CO) 10 (NCMe) 2 , can react two or more times with selected arenes and heteroarenes through a series of CH activations to yield interesting new multiply-CH activated arenes and heteroarenes and can lead to the opening of ring systems in the case of heteroarenes. A summary of these novel reactions and new products is presented in this Frontier article. 

Unprecedented one-step CC bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between “open” corannulene and a strong electron acceptor such as 7,7,8,8-tetracyanoquinodimethane. Alternative to a one-pot solid-state corannulene “unzipping” route, we reported a nine-step solution-based approach for preparation of novel planar “open” corannulene-based derivatives in which electronic structures and photophysical profiles were estimated through the energies and isosurfaces of the frontier natural transition orbitals.