Bonding, aromaticity, and structure of trigonal dianion metal clusters

Giri, Santanab; Roy, Debesh R.; Duley, Soma; Chakraborty, Arindam; Parthasarathi, Ramakrishnan; Elango, M.; Vijayaraj, R.; Subramanian, V.; Islas, Rafael; Merino, Gabriel; Chattaraj, Pratim Kumar

doi:10.1002/jcc.21452

Cited by 37 publications

(26 citation statements)

References 72 publications

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“…As the non‐zero value of the diradical character indicates the propensity of molecule toward triplet state, the molecule is also optimized at the triplet state at the same DFT level of theory. The triplet state is found to be more stable than the singlet state similar to the observation by Giri et al However, the molecule in the triplet state does not show bond‐stretch isomerism like its singlet analogue.…”

Section: Resultssupporting

confidence: 84%

“…In a recent observation by Giri et al, the

{Be}_{3}^{2 -}

which is already known for its exceptional π‐aromatic behaviour, is claimed to be the new inclusion in the family of obscure examples of bond‐stretch isomers . In a number of works, the optimized geometry of

{Be}_{3}^{2 -}

in density functional theory (DFT) is found to come out with D 3 h symmetry where the bond lengths are 2.078 Å .…”

Section: Introductionmentioning

confidence: 99%

“…On the contrary, Sola and coworkers obtained the optimized bond length 2.156 Å with the same D 3 h symmetry of

{Be}_{3}^{2 -}

. This invokes the possibility of existence of bond stretch isomers in planar symmetric

{Be}_{3}^{2 -}

system . Though, the aromaticity in

{Be}_{3}^{2 -}

is well cultivated in the light of all‐metal aromatic clusters, the phenomenon of bond‐stretch isomerism in

{Be}_{3}^{2 -}

is yet to be studied in detail.…”

Section: Introductionmentioning

confidence: 99%

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Unique bonding pattern and resulting bond stretch isomerism in Be32−

Goswami

Paul

Mandal

et al. 2015

Int. J. Quantum Chem.

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The bond‐stretch isomers are characterized by a principal change in the bond‐length with the rest of the molecule being unaltered. The electronic structure regulates the bond stretch isomerism phenomenon in Be32− which has been investigated with density functional theory, ab initio CASSCF, highly efficient n‐electron valence state perturbation theory and multireference configuration interaction calculations. Two isomers are distinguished on different potential energy surfaces and the corresponding avoided crossing is also studied in details. The bonding pattern in two isomers are analysed through adaptive natural density partitioning analysis and quantum theory of atoms in molecules analysis. The bonds in both the isomers primarily involve the 2p orbitals, which overlap face‐to‐face in long‐bond isomer. Whereas, in‐plane π‐bonding occurs at the short‐bond isomer leading to unusual bent bond. © 2015 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 84%

“…In a recent observation by Giri et al, the

{Be}_{3}^{2 -}

{Be}_{3}^{2 -}

in density functional theory (DFT) is found to come out with D 3 h symmetry where the bond lengths are 2.078 Å .…”

Section: Introductionmentioning

confidence: 99%

“…On the contrary, Sola and coworkers obtained the optimized bond length 2.156 Å with the same D 3 h symmetry of

{Be}_{3}^{2 -}

. This invokes the possibility of existence of bond stretch isomers in planar symmetric

{Be}_{3}^{2 -}

system . Though, the aromaticity in

{Be}_{3}^{2 -}

is well cultivated in the light of all‐metal aromatic clusters, the phenomenon of bond‐stretch isomerism in

{Be}_{3}^{2 -}

is yet to be studied in detail.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Unique bonding pattern and resulting bond stretch isomerism in Be32−

Goswami

Paul

Mandal

et al. 2015

Int. J. Quantum Chem.

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“…Interestingly, we found that the singlet state of the isolated cyclo ‐[Mg 3 ] 2− unit has exclusively σ‐aromaticity. Therefore, it seems that the interaction of Na + with this unit triggers off an unprecedented shift from the σ‐aromatic cluster to π‐aromatic species, NaMg 3 − and Na 2 Mg 3 23,121. It is worth mentioning here that the singlet state is not the ground state of cyclo ‐[Mg 3 ] 2− ; several accurate calculations have shown23,122 that actually the triplet state lies about 1–2 kcal/mol below the singlet state.…”

Section: Other Inorganic Clustersmentioning

confidence: 99%

Metalloaromaticity

Feixas

Matito

Poater

et al. 2012

WIREs Comput Mol Sci

113

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In the last decade, the study of aromaticity has experienced enormous progress. The new discoveries, which include species such as the metallabenzenes, heterometallabenzenes, metallabenzynes, metallabenzenoids, metallacyclopentadienes, metallacyclobutadienes, and all‐metal and semimetal clusters, have joined the classical organic aromatic molecules such as benzene, benzenoid and nonbenzenoid polycyclic aromatic hydrocarbons, and heteroaromatic species to conform the current aromatic zoo. These new molecules, which are potentially useful for certain purposes as specific and very efficient catalysts, molecular electronic devices, molecular magnets, drugs, and other as yet unimagined applications, have brought a complete revolution in the field. At variance with the classical aromatic organic molecules that possess only π‐electron delocalization, aromaticity in these new species is much more complex. These compounds have σ‐, π‐, δ‐, and ϕ‐electron delocalization. In addition, they can combine different types of aromaticity thus giving rise to double or triple aromaticity, the so‐called multifold aromaticity. The new molecules can also have conflicting aromaticity, i.e., they can be aromatic in one component and antiaromatic in another. Moreover, most of the old indicators are not valid to discuss the complex aromaticity of these novel compounds. The lack of reliable measures of aromaticity for these systems has triggered the development of new and more general and reliable indices that can be applied to both classical organic and inorganic aromatic compounds. Among them, the use of multicenter electronic delocalization indices is advocated because they help to detect the different types of aromaticity and provide reasonable qualitative orderings of aromaticity. © 2012 John Wiley & Sons, Ltd. This article is categorized under: Structure and Mechanism > Molecular Structures

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“…One of such phenomena is the bond stretch isomerism, the isomer where more than one stable configuration of the same molecule exists with only major distinct difference in the bond length. Many instances of bond stretch isomerization have been theorized or reported for organic, main group elements, and transition metal compounds . Among such structures is the silicon analogues of bicyclo[1.1.0]butane (Scheme a).…”

Section: Introductionmentioning

confidence: 99%

Switchable dual bonding nature in silabicyclo[1.1.0]butanes that exhibit bond stretch isomerism

Chinaroj

Iwamoto

2019

J of Physical Organic Chem

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Silicon analogues of bicyclo[1.1.0]butanes are known to exhibit a bond stretch isomerism where the bridgehead Si Si bond changes in both length and geometry. The bridgehead silicon atom of long bond (lb) isomers exhibits an unusual geometry where all the bonds are located on the same hemisphere, making the geometry of the bridgehead Si Si bond the so-called inverted σ bond in contrast with the typical σ bond geometry found in the short bond (sb) isomers. Herein, the bonding nature of bridgehead Si Si bonds was theoretically investigated in detail using valence bond theory calculation at SL-BOVB/6-31G(d) level of theory. Our calculation demonstrates that the bond type of the bridgehead bond depends on the geometry around the bridgehead atoms with those in sb and lb isomers classified as covalent (COV) and chargeshift (CS) bonds, respectively. The different bond types between two bond stretch isomer indicate that the bonding nature is switchable in one molecule. The detailed examination of the bond stretch isomerization in parent 1,3-disilabicyclo[1.1.0]butane demonstrated that the enhanced CS bond nature in the lb isomer is mainly attributed to the geometry inversion of the σ bond rather than the bond elongation. This switchable dual bonding nature provides an important platform to compare covalent and CS bond on equal footing for both theoretical and experimental investigations. K E Y W O R D Sbicyclo[1.1.0]butane, bond theory, charge shift bond, covalent bond, silicon

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Bonding, aromaticity, and structure of trigonal dianion metal clusters

Cited by 37 publications

References 72 publications

Unique bonding pattern and resulting bond stretch isomerism in Be32−

Unique bonding pattern and resulting bond stretch isomerism in Be32−

Metalloaromaticity

Switchable dual bonding nature in silabicyclo[1.1.0]butanes that exhibit bond stretch isomerism

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