CO2 Activation Within a Superalkali-Doped Fullerene

Abstract

With the aim of finding a suitable synthesizable superalkali species, using the B3LYP/6-31G* density functional level of theory we provide results for the interaction between the buckminsterfullerene C60 and the superalkali Li3F2. We show that this endofullerene is stable and provides a closed environment in which the superalkali can exist and interact with CO2. It is worthwhile to mention that the optimized Li3F2 structure inside C60 is not the most stable C2v isomer found for the “free” superalkali but the D3h geometry. The binding energy at 0 K between C60 and Li3F2 (D3h) is computed to be 119 kJ mol−1. Once CO2 is introduced in the endofullerene, it is activated, and the OCO^ angle is bent to 132°. This activation does not follow the previously studied CO2 reduction by an electron transfer process from the superalkali, but it is rather an actual reaction where a F (from Li3F2) atom is bonded to the CO2. From a thermodynamic analysis, both CO2 and the encapsulated [Li3F2⋅CO2] are destabilized in C60 with solvation energies at 0 K of 147 and < −965 kJ mol−1, respectively.

Superalkalis with Hydrogen as Central Electronegative Atom and their Possible Applications: Ab Initio and DFT Study

“…But the reduction of CO 2 is extremely complex due to the negative electron affinity of carbon dioxide (−0.60±0.2 eV) as observed from Table 4 and large structural reorganization between linear CO 2 and bent CO 2 − anion. However, it was suggested recently that superalkalis can be used to reduce CO 2 into CO 2 − [5–8] . Therefore, it would be interesting to enquire whether the studied superalkalis are capable of transferring electron to carbon dioxide.…”

“…À . [5][6][7][8] Therefore, it would be interesting to enquire whether the studied superalkalis are capable of transferring electron to carbon dioxide. Optimized structures of CO 2 , CO 2 À ion and HLi 2 À CO 2 complexes are depicted in Figure 4.…”

“…[3] Due to their low ionization energies and excellent reducing ability, superalkalis play an important role in chemistry. These species were employed for the reduction and activation of stable compounds [4][5][6][7][8][9][10][11] having low electron affinities (EAs). From previous studies, it is observed that superalkalis were used to devise novel supersalts, [12][13][14] alkalides, [15,16] electrides, [17,18] superbases [19,20] etc., with unique features.…”

Superalkalis for the Activation of Carbon Dioxide: A Review

“…The interaction of CO 2 with the binuclear Li 3 F 2 superalkali was reported by Park and Meloni as discussed in an earlier section. Recently, Meloni et al [44] investigated the interaction of CO 2 with Li 3 F 2 inside fullerene (C 60 ) by using B3LYP [57,58] with the 6-31G (d) basis set in the Gaussian 09 program. They noticed two important features.…”

Reactivity of the superhalogen/superalkali ion encapsulating C60 fullerenes

“…62 Although different varieties of the species of this kind have been reported, 63,64 several studies have been dedicated to lithium-based superalkalis encapsulated in fullerenes. [65][66][67] In this work, we report a mechanistic study of DA reaction involving SA/SH@C60 (SA=Li2F + , SH=LiF2 -) species as the dienophile and 1,3-CHD as diene. The main aim is to determine the effect on the reactivity of the fullerenic cage caused by the encapsulated SA or SH.…”