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

ChemistryOpen

Juan Pablo Martínez¹  Prof. Miquel Solಠ

[1] Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Girona, Catalonia, Spain;ORCID:orcid.org/0000-0002-1917-7450

关键词: density functional theory;    green chemistry;    homogeneous catalysis;    organoboron compounds;    rhodium;    Suzuki–Miyaura;   

DOI  :  10.1002/open.201500093

来源: Wiley

【 摘 要 】

Abstract

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.

【 授权许可】

CC BY-NC-ND   
© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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