Response of D. H. Rouvray and R. B. King, Editors of the Book “The Periodic Table: Into the 21st Century”

King, R. B.; Rouvray, Dennis H.

doi:10.1007/s10698-006-9013-y

Cited by 16 publications

(44 citation statements)

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“…He proposed the term “superaromaticity” to explain the three‐dimensional (3D) aromaticity of

{normalB}_{12} {normalH}_{12}^{2 -}

. Explicitly, the idea of 3D aromaticity of deltahedral boranes was put forward by Aihara and by King and Rouvray in 1978. Further advancement of 3D aromaticity was put forward by Kroto et al who stated “C 60 appears to be aromatic” based on its prominent intensity in mass spectra.…”

Section: Introductionmentioning

confidence: 99%

d‐AO spherical aromaticity in Ce₆O₈

Oganov

Popov

et al. 2015

J Comput Chem

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After the first introduction of π aromaticity in chemistry to explain the bonding, structure, and reactivity of benzene and its derivatives, this concept was further applied to many other compounds featuring other types of aromaticity (i.e., σ, δ). Thus far, there have been no reports on d-AO-based spherical σ aromaticity. Here, we predict a highly stable bare Ce6O8 cluster of a spherical shape using evolutionary algorithm USPEX and DFT + U calculations. Natural bond orbital analysis, adaptive natural density partitioning algorithm, electron localization function, and partial charge plots demonstrate that bare Ce6O8 cluster exhibits d-AO spherical σ aromaticity, thus explaining its exotic geometry and stability. Ce6O8 complex plays an important role in many reactions and is known to exist in many forms, such as in NH4[Ce6(μ(3)O)5(μ(3)OH)3(μ(2)-C6H5COO)9(NO3)3(DMF)3]*DMF*H2O compound, which is prepared under room temperature, and acts as an oxidizing agent.

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“…He proposed the term “superaromaticity” to explain the three‐dimensional (3D) aromaticity of

{normalB}_{12} {normalH}_{12}^{2 -}

Section: Introductionmentioning

confidence: 99%

d‐AO spherical aromaticity in Ce₆O₈

Oganov

Popov

et al. 2015

J Comput Chem

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“…[6,7] The most significant contribution was formulated by Hückel based on the quantum chemical ground in 1931, and the aromaticity is associated with the special stability and property of cyclic planar molecules having delocalized 4n + 2 π electrons. [8,9] However, this concept has undergone a significant transformation over the time and now includes antiaromaticity, [10,11] aromaticity due to delocalized σelectrons, [12] double aromaticity, which suggests delocalization in both σand π-skeletons, [13] three dimensional aromaticity in polyhedral molecules, [14,15] and Mobius Aromaticity. [16,17] Apart from this, the term inorganic aromatics [18,19] was also coined for a special class of molecules, which do not contain any carbon atom in their cyclic structure.…”

Section: Introductionmentioning

confidence: 99%

6π, 8π and 10π Six Membered Sulfur Nitrogen Compounds: A Comparative Study with Organic Analogues

Sadik

Liya

2019

ChemistrySelect

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Benzene has played an important role in the development of the ideas concerning ′aromaticity′, as much as that benzene and its derivatives are the best examples of aromatic compounds. Although the inorganic aromatic compounds have been found to obey Hückel 4n+2 π electron rule, they often possess a different number of πe as compared to their organic analogues. One such system is cyclic compounds of S3N3, where 10 π aromatic S3N3− and 8π S3N3+ are known, but interestingly, a 6π benzene‐analogue of the sulfur‐nitrogen compound is not reported. Hence as a case study, we have undertaken an extensive theoretical investigation of the electronic structure of 6π, 8π and 10π electrons cyclic S3N33+, S3N3+ and S3N3−, based on the Energy Decomposition Analysis (EDA). We have also compared the results with isoelectronic classical C6H6, C6H62− and C6H64−. Our results indicated that the π‐contribution increases and the σ‐contribution decreases, while the contribution from the orbital interaction energy remains nearly similar upon addition of π electrons to C6H6 and S3N33+. However, the major decrease in the interaction energy is caused by the drastic reduction of the electrostatic component in C6H64− and S3N33+, which can be correlated to the instability of these molecules. Thus, aromatic binary compounds of sulfur and nitrogen are commonly π‐electron rich, while their aromatic hydrocarbon analogues are π‐electron precise.

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“…For closo deltahedra having from 6 to 12 vertices this means only degree 4 and degree 5 vertices except for a single topologically required degree 6 vertex in the most spherical 11‐vertex deltahedron, sometimes confusingly called an “edge‐coalesced icosahedron.” Closo borane deltahedra with n vertices are characterized by 2 n + 2 skeletal electrons, as embodied in the Wade–Mingos rules . Graph‐theory based topological approaches were developed to rationalize the Wade–Mingos rules requiring 2 n + 2 skeletal electrons for closo deltahedral borane structures …”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13] Graph-theory based topological approaches were developed to rationalize the Wade-Mingos rules requiring 2n 1 2 skeletal electrons for closo deltahedral borane structures. [14] The further development of metallaborane chemistry, particularly by Kennedy and coworkers, [15][16][17][18] led to the discovery of 9-and 10-vertex metallaboranes based on deltahedra topologically distinct from closo deltahedra. Such chemistry most frequently involves the second and third row transition metals and leads to slightly hypoelectronic n-vertex structures having 2n rather than the Wadean 2n 1 2 skeletal electrons.…”

Section: Introductionmentioning

confidence: 99%

Molybdatricarbaboranes as examples of isocloso metallaborane deltahedra with three carbon vertices

Lupan

King

2015

J Comput Chem

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Density functional theory shows that the lowest energy CpMoC3B(n-4)H(n-1) (n = 8, 9, 10, 11) structures are based on isocloso or similar deltahedra with the molybdenum atom at a degree 6 vertex. Such deltahedra include the capped pentagonal bipyramid for the 8-vertex system. Among such geometries the lowest energy structures have the carbon atoms at the lowest degree vertices (typically degree 4 vertices), no pairs of adjacent carbon atoms (i.e., no C-C edges), and the maximum number of Mo-C edges. Optimizing these factors favoring low-energy CpMoC3B(n-4)H(n-1) (n = 8, 9, 10, 11) structures leads to a unique lowest energy structure lying more than 10 kcal/mol below the next lowest energy structure for the 8-, 10-, and 11-vertex systems. However, the 9-vertex CpMoC3B5H8 system has three structures within 8 kcal/mol including a structure based on the closo tricapped trigonal prism rather than the isocloso 9-vertex deltahedron.

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Response of D. H. Rouvray and R. B. King, Editors of the Book “The Periodic Table: Into the 21st Century”

Cited by 16 publications

References 0 publications

d‐AO spherical aromaticity in Ce₆O₈

d‐AO spherical aromaticity in Ce₆O₈

6π, 8π and 10π Six Membered Sulfur Nitrogen Compounds: A Comparative Study with Organic Analogues

Molybdatricarbaboranes as examples of isocloso metallaborane deltahedra with three carbon vertices

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Response of D. H. Rouvray and R. B. King, Editors of the Book “The Periodic Table: Into the 21st Century”

Cited by 16 publications

References 0 publications

d‐AO spherical aromaticity in Ce6O8

d‐AO spherical aromaticity in Ce6O8

6π, 8π and 10π Six Membered Sulfur Nitrogen Compounds: A Comparative Study with Organic Analogues

Molybdatricarbaboranes as examples of isocloso metallaborane deltahedra with three carbon vertices

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d‐AO spherical aromaticity in Ce₆O₈

d‐AO spherical aromaticity in Ce₆O₈