Coordination complexes of P^III-doped heterobuckybowls and their applications in catalysis

Doping the π-frameworks of polycyclic aromatic hydrocarbons (PAHs) with main-group elements is a powerful strategy to manipulate optoelectronic properties. Herein, the benzylic carbons of π-bowl sumanene are replaced with chalcogens (S, Se, and Te) and trivalent phosphorus (P^III), affording a series of P^III-doped heterosumanenes (HSEs). The lone-pair electrons of the P^III-dopant endow these HSEs with pronounced affinity toward transition metals (Au⁺, Pt²⁺, and Pd²⁺). Accordingly, nine coordination complexes were synthesized to exhibit diverse coordination patterns contingent upon the metal ions and chalcogen atoms on HSEs. For the first time, we proved that the Pd²⁺ complexes of these HSEs are promising catalysts for the Suzuki-Miyaura coupling reaction of aryl chlorides.