Chemical applications of group theory and topology. 7. A graph-theoretical interpretation of the bonding topology in polyhedral boranes, carboranes, and metal clusters

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

doi:10.1021/ja00466a014

Cited by 238 publications

(94 citation statements)

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“…We calculated the thermodynamic parameters of isomerization reactions of carboranes (12) (2) in the B3LYP/6 311G(2d,2p) approximation for the tem perature range 298-1000 K and a pressure of 1 atm. Analysis of the results obtained ( Fig.…”

Section: Resultsmentioning

confidence: 99%

Structure and properties of 1,2-, 1,7-, and 1,12-dicarba-closo-dodecaboranes(12): A quantum chemical study

2006

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The molecular and electronic structures and thermodynamic parameters of 1,2 , 1,7 , and 1,12 dicarba closo dodecaborane(12) molecules in the singlet ground state were calculated by the Hartree-Fock, DFT, and MP2 (including B3LYP/6 311G(2d,2p) and MP2/6 311+G(d,2p) methods). The energies and character of spatial localization of the fron tier MOs in o , m , p carboranes(12) correlate with the changes in the configuration stabilities and reactivities in the reactions of carboranes with electrophilic and nucleophilic agents and bases. The electrostatic potential distributions in the molecules and the atomic charge distribu tion of hydrogen atoms correlate with the known chemical properties of carboranes(12). The thermodynamic parameters of two isomerization reactions, o C 2 B 10 H 12 m C 2 B 10 H 12 and m C 2 B 10 H 12 p C 2 B 10 H 12 , calculated for the temperature range 298-1000 K agree with experimental data within the limits of measuring error. The values of the electron density and the Laplacian of the electron density at the (3, -1) critical points of the B-H and C-H bonds correlate with the reactivities of the title compounds.The electronic structures of closo carboranes(12), C 2 B 10 H 12 , and their derivatives has been studied by theo retical 1-8 and experimental 9 methods. In most cases the results of calculations of the molecular structures and relative stabilities of these compounds are compared with the experimental data. Only a few attempts to relate the electronic structure characteristics to the configuration stability, regularities of the electrophilic and nucleo philic reactions, and the acidities of carboranes were re ported. 10-12 Usually, the Mulliken charges on the cage atoms are used as a criterion for assessment of the reactiv ity. 10,12 However, this is not always true when studying the title compounds. 1 Analysis of the electron density distribution function in the vicinity of reaction centers is of paramount importance; 12 however, the computational cost of such calculations is very high. Advances made in this field of chemistry of boranes and carboranes have been documented in a review. 8 In this work we carried out the HF, DFT, and MP2 (including B3LYP/6 311G(2d,2p) and MP2/6 311+G(d,2p)) quantum chemical calculations and determined the thermodynamic characteristics of the isomers of carboranes(12) for the temperature range 298-1000 K and established parameters of their ground state electronic structure, which correlate with the con figuration stability and with characteristic features of elec trophilic and nucleophilic reactions. These are the ener gies and the structures of the frontier MOs, the electro static potential, the atomic charges of hydrogens in the molecules under study, and the characteristics of the total electron density function at the (3, -1) critical points of the B-H and C-H bonds. Calculation ProcedureQuantum chemical calculations of the molecules of o , m , and p carboranes were carried out by the Hartree-Fock and density functional (B3LYP) methods, at the second o...

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Section: Resultsmentioning

confidence: 99%

Structure and properties of 1,2-, 1,7-, and 1,12-dicarba-closo-dodecaboranes(12): A quantum chemical study

2006

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“…The special significance of 2n + 2 skeletal electrons in the Wade-Mingos rules [17][18][19] for determining special stability of deltahedral boranes and carboranes can be rationalized by an approach originating from graph theory [21]. Thus consider a deltahedral borane B n H 2À n or isoelectronic carborane with n vertices.…”

Section: Metal-free Deltahedral Boranes and Carboranesmentioning

confidence: 99%

Geometry and chemical bonding in polyhedral boranes, metallaboranes, and dimetallaboranes: From closo to isocloso to oblatocloso polyhedra

King¹

2009

Journal of Organometallic Chemistry

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“…The combination of the surface and core bonding leads to a total of n + 1 bonding orbitals. Filling each of these bonding orbitals with an electron pair leads to the 2n + 2 skeletal electrons required by the Wade-Mingos rules [11][12][13][14] for a globally delocalized three-dimensional aromatic system [21,22].…”

Section: The Three-dimensional Aromaticity In Polyhedral Boranes and mentioning

confidence: 99%

“…Such deltahedra are often called closo deltahedra. However, there is nothing about the model for three-dimensional aromaticity in boranes [21] presented above that requires the underlying polyhedron to be a deltahedron, i.e., to have all faces triangles. In fact, the three-dimensional aromaticity model does not consider any aspects of the detailed topology of the polyhedron, i.e.…”

Section: The Three-dimensional Aromaticity In Polyhedral Boranes and mentioning

confidence: 99%

Supraicosahedral polyhedra in carboranes and metallacarboranes: The role of local vertex environments in determining polyhedral topology and the anomaly of 13-vertex closo polyhedra

King

2007

Journal of Organometallic Chemistry

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Chemical applications of group theory and topology. 7. A graph-theoretical interpretation of the bonding topology in polyhedral boranes, carboranes, and metal clusters

Cited by 238 publications

References 1 publication

Structure and properties of 1,2-, 1,7-, and 1,12-dicarba-closo-dodecaboranes(12): A quantum chemical study

Structure and properties of 1,2-, 1,7-, and 1,12-dicarba-closo-dodecaboranes(12): A quantum chemical study

Geometry and chemical bonding in polyhedral boranes, metallaboranes, and dimetallaboranes: From closo to isocloso to oblatocloso polyhedra

Supraicosahedral polyhedra in carboranes and metallacarboranes: The role of local vertex environments in determining polyhedral topology and the anomaly of 13-vertex closo polyhedra

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