Chemical bonding in the hexamethylbenzene–SO                         2+                          dication

Lisa Pecher; Sudip Pan; Gernot Frenking

doi:10.1007/s00214-019-2434-1

Chemical bonding in the hexamethylbenzene–SO ²⁺ dication

Lisa Pecher, Sudip Pan, Gernot Frenking

University of Marburg

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

A thorough bonding analysis is performed on the dication [C ₆ (CH ₃ ) ₆ SO] ²⁺ . The results show that the molecule is best described in terms of covalent interactions between the cations C ₆ (CH3) ₆ ⁺ and SO ⁺ , whereby the bonding consists of two dominating contributions. The strongest bonding comes from dative interaction from the HOMO of C ₆ (CH ₃ ) ₆ ⁺ to the LUMO of SO ⁺ , which has overall σ symmetry. The second significant component is due to electron-sharing bonding between the singly occupied orbitals of the two fragments. The bonding situation may be sketched with the formula [C6(CH)6-→SO]2+. The bare dication is thermodynamically unstable with regard to dissociation into two cations. It is kinetically stable due to the activation barrier, and it is further stabilized by counterions.

Original language	English
Article number	47
Journal	Theoretical Chemistry Accounts
Volume	138
Issue number	3
DOIs	https://doi.org/10.1007/s00214-019-2434-1
State	Published - 1 Mar 2019
Externally published	Yes

Keywords

Bonding analysis
Density functional theory
Oxidation state
Small-molecule activation
Sulfur chemistry

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10.1007/s00214-019-2434-1

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title = " Chemical bonding in the hexamethylbenzene–SO 2+ dication ",

abstract = " A thorough bonding analysis is performed on the dication [C 6 (CH 3 ) 6 SO] 2+ . The results show that the molecule is best described in terms of covalent interactions between the cations C 6 (CH3) 6 + and SO + , whereby the bonding consists of two dominating contributions. The strongest bonding comes from dative interaction from the HOMO of C 6 (CH 3 ) 6 + to the LUMO of SO + , which has overall σ symmetry. The second significant component is due to electron-sharing bonding between the singly occupied orbitals of the two fragments. The bonding situation may be sketched with the formula [C6(CH)6-→SO]2+. The bare dication is thermodynamically unstable with regard to dissociation into two cations. It is kinetically stable due to the activation barrier, and it is further stabilized by counterions.",

keywords = "Bonding analysis, Density functional theory, Oxidation state, Small-molecule activation, Sulfur chemistry",

author = "Lisa Pecher and Sudip Pan and Gernot Frenking",

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AU - Pecher, Lisa

AU - Pan, Sudip

AU - Frenking, Gernot

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N2 - A thorough bonding analysis is performed on the dication [C 6 (CH 3 ) 6 SO] 2+ . The results show that the molecule is best described in terms of covalent interactions between the cations C 6 (CH3) 6 + and SO + , whereby the bonding consists of two dominating contributions. The strongest bonding comes from dative interaction from the HOMO of C 6 (CH 3 ) 6 + to the LUMO of SO + , which has overall σ symmetry. The second significant component is due to electron-sharing bonding between the singly occupied orbitals of the two fragments. The bonding situation may be sketched with the formula [C6(CH)6-→SO]2+. The bare dication is thermodynamically unstable with regard to dissociation into two cations. It is kinetically stable due to the activation barrier, and it is further stabilized by counterions.

AB - A thorough bonding analysis is performed on the dication [C 6 (CH 3 ) 6 SO] 2+ . The results show that the molecule is best described in terms of covalent interactions between the cations C 6 (CH3) 6 + and SO + , whereby the bonding consists of two dominating contributions. The strongest bonding comes from dative interaction from the HOMO of C 6 (CH 3 ) 6 + to the LUMO of SO + , which has overall σ symmetry. The second significant component is due to electron-sharing bonding between the singly occupied orbitals of the two fragments. The bonding situation may be sketched with the formula [C6(CH)6-→SO]2+. The bare dication is thermodynamically unstable with regard to dissociation into two cations. It is kinetically stable due to the activation barrier, and it is further stabilized by counterions.

KW - Bonding analysis

KW - Density functional theory

KW - Oxidation state

KW - Small-molecule activation

KW - Sulfur chemistry

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Chemical bonding in the hexamethylbenzene–SO ²⁺ dication

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Keywords

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