On the Reaction Mechanism of the Rhodium‐Catalyzed Arylation of Fullerene (C60) with Organoboron Compounds in the Presence of Water

Density functional theory (DFT) calculations were carried out to study the reaction mechanism of the Suzuki–Miyaura rhodium‐catalyzed hydroarylation of fullerene (C60) by phenylboronic acid in the presence of water. As found experimentally, our results confirm that addition of the phenyl group and the hydrogen atom in C60 occurs at the [6,6] bond. The rate‐determining step corresponds to the simultaneous transfer of a hydrogen atom from a water molecule to C60 and the recovery of the active species. The use of 2‐phenyl‐1,3,2‐dioxaborinane and the 4,4,5,5‐tetramethyl‐2‐phenyl‐1,3,2,‐dioxaborolane instead of phenylboronic acid as organoborate agents does not lead to great modifications of the energy profile. The possible higher steric hindrance of 4,4,5,5‐tetramethyl‐2‐phenyl‐1,3,2,‐dioxaborolane should not inhibit its use in the hydroarylation of C60. Overall, we show how organoboron species arylate C60 in rhodium‐based catalysis assisted by water as a source of protons. Density functional theory (DFT) calculations were used to investigate how organoboron species arylate C60 in rhodium‐based catalysis assisted by water as a source of protons. The computational results support previously determined experimental data that show that the addition of the phenyl group and the hydrogen atom in C60 occurs at the [6,6] bond.