An ab initio valence bond (VB) calculation of the π delocalization energy in borazine, B3N3H6

Benker, Daniel; Klapötke, Thomas M.; Kuhn, Gerhard; Li, Jiabo; Miller, Christian

doi:10.1002/hc.20095

Cited by 27 publications

(24 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Borazine (1), which is known as "inorganic benzene" due to the characteristics of its boron nitride unit [1], has been calculated to be of substantial aromatic character, assuming that resonance energy can be used as a measure of aromaticity [2]. Some diazadiborine isomers have been studied using MNDO (modified neglect of diatomic overlap) calculations (Scheme 1).…”

mentioning

confidence: 99%

Synthesis and structures of monocyclic 1,4-diaza-2,3-diborine species

Söyleyici

Uyanık

Sevinçek

et al. 2015

Inorganic Chemistry Communications

View full text Add to dashboard Cite

mentioning

confidence: 99%

Synthesis and structures of monocyclic 1,4-diaza-2,3-diborine species

Söyleyici

Uyanık

Sevinçek

et al. 2015

Inorganic Chemistry Communications

View full text Add to dashboard Cite

“…Benker et al performed a series of valence bond calculations for borazine and for benzene in order to determine the relative weights of individual standard Lewis structures [12] In the delocalized resonance scheme of borazine, the structure without double bonds and with three lone electron pairs at the three nitrogen atoms is the major contributor with a structural weight of 0.17, followed by six equivalent Lewis structures with one double bond and two lone pairs at two nitrogen atoms with weights of 0.08 each. They estimated the values of 54.1 and 45.8 kcal mol -1 for the delocalization energies of borazine and benzene, respectively.…”

Section: Introductionmentioning

confidence: 99%

Borazine: to be or not to be aromatic

et al. 2007

View full text Add to dashboard Cite

Aromaticity of borazine, which has been subject of controversial discussions, is addressed. Beside a short review on aromaticity of borazine we report a detailed analysis of two molecular fields, the induced magnetic field (B ind ) and the electron localization function (ELF). The induced magnetic field of borazine shows a long-range shielding cone perpendicular to the molecular plane, as in benzene, but lower in magnitude. Contrary to benzene, borazine shows two weakly paratropic regions, one of them inside the ring, and the second one enveloping the boron atoms. It is necessary to separate r and p contributions to identify whether borazine exhibits p-aromatic character comparable to benzene. Nucleus-independent chemical shift (NICS) isolines show that the r electrons are much stronger localized than p electrons, their local paramagnetic contributions generate a short-range response and a paratropic (deshielding) region in the ring center (similar to an anti-aromatic response). Three regions can be identified as chemically meaningful domains exhibiting an internally strong electron delocalization (ELF = 0.823). Borazine may be described as a p aromatic compound, but it is not a globally aromatic species, as the electronic system is not as delocalized as in benzene.

show abstract

“…The present essay will start in next section with some remarks on multireference systems and on localized and delocalized treatments of chemical bonding. This discussion is based both on calculations from the early days of quantum mechanics1, 32–34 and quantum chemistry35, 36 and also on modern computational valence bond theory,13, 37–113 which provides insight into the question of how localized and semilocalized orbitals arise in the treatment of so‐called multireference systems. The section after that presents remarks on the use of VB formalisms and concepts for semiempirical treatments of potential energy surfaces for electronically adiabatic reactions.…”

Section: Introductionmentioning

confidence: 99%

Valence bond theory for chemical dynamics

Truhlar

2006

J Comput Chem

108

View full text Add to dashboard Cite

This essay provides a perspective on several issues in valence bond theory: the physical significance of semilocal bonding orbitals, the capability of valence bond concepts to explain systems with multireferences character, the use of valence bond theory to provide analytical representations of potential energy surfaces for chemical dynamics by the method of semiempirical valence bond potential energy surfaces (an early example of specific reaction parameters), by multiconfiguration molecular mechanics, by the combined valence bond-molecular mechanics method, and by the use of valence bond states as coupled diabatic states for describing electronically nonadiabatic processes (photochemistry). The essay includes both ab initio and semiempirical approaches.

show abstract

An ab initio valence bond (VB) calculation of the π delocalization energy in borazine, B₃N₃H₆

Cited by 27 publications

References 38 publications

Synthesis and structures of monocyclic 1,4-diaza-2,3-diborine species

Synthesis and structures of monocyclic 1,4-diaza-2,3-diborine species

Borazine: to be or not to be aromatic

Valence bond theory for chemical dynamics

Contact Info

Product

Resources

About