Normal coordinates, structure, and bonding of benzyne

Laing, Jean Wilcox; Berry, R. Stephen

doi:10.1021/ja00419a004

Cited by 39 publications

(14 citation statements)

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“…Ever since their first demonstration the relative contributions of the resonance structures of arynes have remained unclear 41 . We investigated thoroughly the data in Fig.…”

Section: Resultsmentioning

confidence: 99%

On-surface generation and imaging of arynes by atomic force microscopy

et al. 2015

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Reactive intermediates are involved in many chemical transformations. However, their characterization is a great challenge because of their short lifetimes and high reactivities. Arynes, formally derived from arenes by the removal of two hydrogen atoms from adjacent carbon atoms, are prominent reactive intermediates that have been hypothesized for more than a century. Their rich chemistry enables a widespread use in synthetic chemistry, as they are advantageous building blocks for the construction of polycyclic compounds that contain aromatic rings. Here, we demonstrate the generation and characterization of individual polycyclic aryne molecules on an ultrathin insulating film by means of low-temperature scanning tunnelling microscopy and atomic force microscopy. Bond-order analysis suggests that a cumulene resonance structure is the dominant one, and the aryne reactivity is preserved at cryogenic temperatures. Our results provide important insights into the chemistry of these elusive intermediates and their potential application in the field of on-surface synthesis.

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“…Ever since their first demonstration the relative contributions of the resonance structures of arynes have remained unclear 41 . We investigated thoroughly the data in Fig.…”

Section: Resultsmentioning

confidence: 99%

On-surface generation and imaging of arynes by atomic force microscopy

et al. 2015

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“…Two normal coordinate analyses based on these results have been reported. 21,22 The connection between the electrophilicity of o-benzyne and its strained acetylenic bond has been investigated by Houk, Jordan, Krebs, and co-workers,23"25 using a combination of theoretical and spectroscopic methods. Ab initio24,26 and extended Httckel27 calculations of acetylene indicate a dramatic stabilization of the lowest unoccupied molecular orbital (LUMO) on cis bending of the molecule.…”

Section: Introductionmentioning

confidence: 99%

Determination of the singlet-triplet splitting and electron affinity of o-benzyne by negative ion photoelectron spectroscopy

1986

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“…simply being like benzene except for an additional weak bond composed of two overlapping sp 2 orbitals [30]. Later, Laing and Berry studied o-benzyne via matrix isolation and reported this`triple bond' to have a length of 1.35 A Ê (which is slightly shorter than the 1.40 A Ê for a typical benzene CÐ C bond) [31]; however, a recent experimental estimate of 1.24 6 0.02 A Ê has been given by Orendt et al [32]. In 1992, the ® rst complete infrared (IR) spectrum of o-benzyne was reported by Radziszewski et al [33].…”

Section: Resultsmentioning

confidence: 99%

Medium ring compounds and their anions: a systematic density functional theory study

DEBRA¹

1998

Molecular Physics

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The optimized geometries, harmonic vibrational frequencies, and adiabatic electron a nities of eight ring compounds: o-benzyne, cyclohexanone enolate, cyclopentadienyl radical, cyclopentanone enolate, maleic anhydride, phenoxyl radical, phenyl radical, and pyrrolyl radical have been determined with six di erent density functional or hybrid Hartree± Fock density functional methods using a double-zeta basis set with polarization and di use functions (DZP+ + ). The optimized geometric structures are discussed. Harmonic vibrational frequencies were generally found to be within 4% of available experimental fundamentals for most functionals. Of the six functionals, BP86 predicted electron a nities remarkably close to the experimental values for six of the eight molecules studied, with an overall average absolute error with respect to experiment of just 0.12 eV. The B3LYP and BLYP functionals also gave excellent predictions, with absolute average errors of 0.18 and 0.20 eV, respectively.

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Normal coordinates, structure, and bonding of benzyne

Cited by 39 publications

References 3 publications

On-surface generation and imaging of arynes by atomic force microscopy

On-surface generation and imaging of arynes by atomic force microscopy

Determination of the singlet-triplet splitting and electron affinity of o-benzyne by negative ion photoelectron spectroscopy

Medium ring compounds and their anions: a systematic density functional theory study

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