Quantum‐chemical approaches in the study of fullerene and its derivatives by the example of the most typical cycloaddition reactions: A review

Abstract

In the past two decades, quantum chemistry has become an indispensable tool for the reliable interpretation of experimental measurements of a wide range of molecular properties of fullerene and its derivatives. Among the modern quantum-chemical methods of analysis, preference is given to the density functional theory. This review describes the computational studies that demonstrate rather comprehensively the prospects of quantum-chemical calculations in many fields of the chemistry of fullerene and its derivatives, such as geometric parameters, stability of structures, molecular spectroscopic properties, electronic structures, the nature of bonds, thermochemistry, and simulation of the kinetics and mechanism of processes. The review focuses on the most typical cycloaddition reactions such as Diels-Alder, Prato and Bingel-Hirsch reactions.The general trends of scientific studies in this area are also discussed and a wide range of references is provided where the readers can find technical details of computational approaches that may be of interest for them.

How Does Spin Play with the Cycloaddition to Paramagnetic Endohedral Metallofullerenes? The Curious Case of TiSc2N@C80

“…We performed all DFT calculations with the BP86 functional − including Grimme’s DFT-D3 dispersion correction with Becke–Johnson damping, as implemented in the Gaussian 16 suite of programs . This functional has been commonly used for the study of the thermodynamics and reactivity of EMFs. , We also employed the Perdew–Burke–Ernzerhof (PBE) functional ,− with the same D3­(BJ) dispersion correction scheme and tested some typical cases in this work. As shown by the detailed assessment in Section 2 in the Supporting Information, the PBE functional produced results in reasonable agreement with those given by the BP86 functional.…”

“…Diels–Alder (DA) cycloaddition is one of the most powerful reactions for the exohedral functionalization of fullerenes − and endohedral metallofullerenes (EMFs , ). − Compared to neutral empty fullerenes, EMFs are generally believed to have a much reduced reactivity toward the DA reaction due to the electron transfer from the metal cluster to the carbon cage. − The negative charge on the EMF cage significantly elevates its lowest-unoccupied molecular orbitals (LUMOs) and consequently hampers the electron flow from the diene to fullerene in a normal demand DA addition …”

Isosterism in pyrrole via azaboroles substitution, a theoretical investigation for electronic structural, stability and aromaticity

“…Furthermore, numerous studies have considered the influence of incorporating Boron Nitrogen into fullerene and nanotube frameworks [ [41] , [42] , [43] ]. The introduction of hetero-atoms such as boron or nitrogen into carbon nanotubes offers the possibility of tailoring their structural and electronic properties.…”

Barrier Heights for Diels–Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules

“…Studies of cycloaddition reactions have a long history. − In a recent work, Jamieson et al studied, among other related reactions, the ambimodal [6 + 4] cycloaddition of tropone with cycloheptatriene. Key transition states ( TS8 and TS9 , where we use their numbering for all species, and we put the zero of energy at the overall reactants, as they do) are the transition states for [4 + 2] Diels–Alder reactions leading from intermediates to the final pentacyclic products, whose structures are 11 and 12 .…”