A Complex Containing Four Magnesium Atoms and Two Mg–Mg Bonds Behaving as an Electride

Saha, Ranajit; Das, Prasenjit; Chattaraj, Pratim Kumar

doi:10.1002/ejic.201900813

Cited by 17 publications

(25 citation statements)

References 65 publications

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“…(see Table 4), respectively. The β value is zero because of the symmetry of the system 17,84 . A comparison of NLO properties of Mg 2 @C 60 with previously known electrides, for example, M@calix (M = Li, Na; calix = calix[4]pyrrole), 13 Li@B 10 H 14 85 and M 2 (TCNQ) 14 (M = Li, Na; TCNQ = Tetracyanoquinodimethane), Mg 2 EP (EP = 3.1.3.1)) have been carried out and presented in Table S5.…”

Section: Nature Of Bondingmentioning

confidence: 99%

Encapsulation of Mg₂inside a C₆₀cage forms an electride

2020

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Density functional theory (DFT) based calculations have been carried out for the endohedral encapsulation of magnesium dimer inside fullerene, that is, Mg 2 @C 60 . It is observed that the minimum energy structure of the Mg 2 @C 60 system is C 2h symmetry. The Mg Mg bond distance in the Mg 2 @C 60 system is much shorter than that in the free Mg 2 and Mg 2 2+ ion. The formation of the endohedral Mg 2 @C 60 system is thermochemically spontaneous in nature. The natural bond orbital (NBO) analysis showed the presence of an Mg 2 2+ fragment with an Mg Mg bond inside the C 60 cage. The electron density descriptors have identified the covalency in the Mg Mg bond. A non-nuclear attractor (NNA) is present in the middle of the two Mg-atoms. The bonding interaction between the Mg 2 and C 60 fragments is ionic in nature and the [Mg 2 2+ ] and [C 60 2− ] represent the bonding pattern in the Mg 2 @C 60 system. The designed endohedrally encapsulated system behaves as an electride. K E Y W O R D S electride, electron localization function (ELF) basin, endohedrally encapsulated fullerene, energy decomposition analysis (EDA), non-nuclear attractor (NNA)

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Section: Nature Of Bondingmentioning

confidence: 99%

Encapsulation of Mg₂inside a C₆₀cage forms an electride

2020

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“…The numerical values of the NLO properties have been given in Table . As the geometries of all the complexes are symmetric, the β values are zero. , Mg 2 (η 5 -C 5 I 5 ) 2 complex shows the highest values of α̅ and the highest γ ∥ values shown by Mg 2 (η 5 -C 5 Me 5 ) 2 complex. So, most of the substituent groups affect the NLO properties.…”

Section: Resultsmentioning

confidence: 97%

Substituent Effects on Electride Characteristics of Mg₂(η⁵-C₅H₅)₂: A Theoretical Study

Das

Chattaraj

2021

J. Phys. Chem. A

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An ab initio study has been carried out on the substituted binuclear sandwich complexes of Mg 2 (η 5 -C 5 H 5 ) 2 . We have checked whether the substitution destroys the electride properties of a complex, as it needs to satisfy several stringent criteria to obtain the status of an electride. The thermochemical results show that the complexes are stable at room temperature and 1 atm pressure. From the analysis of the various electron density descriptors and the natural bond orbital (NBO) for all the complexes, it is confirmed that the Mg−Mg bonds are covalent and the metal−ligand bonds are ionic in nature. The charges on each Mg atom in the studied complexes are +1. Analysis of the electron density descriptors shows the presence of a non-nuclear attractor (NNA) at the middle of the bond formed by the two Mg atoms when attached to the ligands. The electride characteristics are exhibited by all of the designed complexes. We also report the aromaticity behavior and reactivity descriptors of these complexes. The electride characteristics of Mg 2 (η 5 -C 5 H 5 ) 2 complex get affected on substitution, as both the NNA population and the nonlinear optical properties (NLO) of the complexes are changed.

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“…The donation of the loosely trapped electron to antibonding MOs of certain bonds in small molecules (H-H in H 2 , C-O in CO 2 , N-O in N 2 O, and C-H in CH 4 and C 6 H 6 ) results in the activation followed by the dissociation of the respective bonds (Saha and Chattaraj, 2018). Another study (Saha et al, 2019) performed by our group utilizes the modified form of β-diketiminate ligand ( Dipp Nacnac) to hold four Mg atoms with two equivalent Mg(I)-Mg(I) bonds ([Mg 4 ( Dipp H L) 2 ] 2-) in its lower energy singlet state. Two NNAs are found to be present at the center of each Mg(I)-Mg(I) bond with an electron population of 1.18 |e| and 52% localization.…”

Section: Structure Bonding and Reactivity Of Various Molecular Electridesmentioning

confidence: 99%

Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics

2021

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Atomic clusters lie somewhere in between isolated atoms and extended solids with distinctly different reactivity patterns. They are known to be useful as catalysts facilitating several reactions of industrial importance. Various machine learning based techniques have been adopted in generating their global minimum energy structures. Bond-stretch isomerism, aromatic stabilization, Rener-Teller effect, improved superhalogen/superalkali properties, and electride characteristics are some of the hallmarks of these clusters. Different all-metal and nonmetal clusters exhibit a variety of aromatic characteristics. Some of these clusters are dynamically stable as exemplified through their fluxional behavior. Several of these cluster cavitands are found to be agents for effective confinement. The confined media cause drastic changes in bonding, reactivity, and other properties, for example, bonding between two noble gas atoms, and remarkable acceleration in the rate of a chemical reaction under confinement. They have potential to be good hydrogen storage materials and also to activate small molecules for various purposes. Many atomic clusters show exceptional opto-electronic, magnetic, and nonlinear optical properties. In this Review article, we intend to highlight all these aspects.

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A Complex Containing Four Magnesium Atoms and Two Mg–Mg Bonds Behaving as an Electride

Cited by 17 publications

References 65 publications

Encapsulation of Mg₂inside a C₆₀cage forms an electride

Encapsulation of Mg₂inside a C₆₀cage forms an electride

Substituent Effects on Electride Characteristics of Mg₂(η⁵-C₅H₅)₂: A Theoretical Study

Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics

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A Complex Containing Four Magnesium Atoms and Two Mg–Mg Bonds Behaving as an Electride

Cited by 17 publications

References 65 publications

Encapsulation of Mg2inside a C60cage forms an electride

Encapsulation of Mg2inside a C60cage forms an electride

Substituent Effects on Electride Characteristics of Mg2(η5-C5H5)2: A Theoretical Study

Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics

Contact Info

Product

Resources

About

Encapsulation of Mg₂inside a C₆₀cage forms an electride

Encapsulation of Mg₂inside a C₆₀cage forms an electride

Substituent Effects on Electride Characteristics of Mg₂(η⁵-C₅H₅)₂: A Theoretical Study