The norbornene mystery revealed

Steinmann, Stephan N.; Vogel, Pierre; Mo, Yirong; Corminbœuf, Clémence

doi:10.1039/c0cc00601g

Cited by 30 publications

(41 citation statements)

References 26 publications

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“…This parallels the enhanced reactivity and electron density of the five-ring side of norbornene. 7,8 Again, a complex band pattern further red-shifted by 20−40 cm −1 behaves like No-rich complexes with one T unit embedded. However, there is now a single narrow transition that is only red-shifted by 14 cm −1 from TNo 5 .…”

Section: ■ Experimental Resultsmentioning

confidence: 96%

Molecular Docking via Olefinic OH···π Interactions: A Bulky Alkene Model System and Its Cooperativity

2014

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Complexes of t-butyl alcohol with norbornene and its monocyclic constituents cyclopentene and cyclohexene are studied via their OH stretching fundamental transitions in supersonic jet expansions. Compared to OH···OH hydrogen bonds, the spectral shifts due to OH···π bonding in the mixed dimers are reduced by a factor of 2. Mixed trimers show substantially different spectral signatures due to cooperative effects. Regioselective docking on the two sides of the double bond in norbornene is observed. Harmonic modeling of the spectra using dispersion-corrected hybrid functionals is quite successful, suggesting a high predictive power for this poorly explored class of complexes between alcohols and alkenes.

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Section: ■ Experimental Resultsmentioning

confidence: 96%

Molecular Docking via Olefinic OH···π Interactions: A Bulky Alkene Model System and Its Cooperativity

2014

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“…33,51 The later functional feature OPTZ exchange, which assists in the accurate reproduction of energies of inorganic complexes with different spin states. [52][53][54] The M06/def2-SVP geometries of relevant compounds were then recomputed as single point energies using a density-dependent dispersion correction [35][36][37][38] appended to the PBE0 33,34 functional (PBE0-dDsC) with the triple- slater-type orbital TZ2P basis set in ADF. 55,56 Solvation corrections (in THF) employed the continuum solvent model for realistic solvents 41 (COSMO-RS), as implemented in ADF.…”

Section: Computational Detailsmentioning

confidence: 99%

“…To elucidate additional mechanistic details we employed density functional theory computations at the PBE0 33,34 -dDsC [35][36][37][38] /TZ2P//M06 39,40 /def2-SVP level to determine the reaction free energy profiles in implicit THF solvent (using the COSMO-RS 41 solvation model) of the bimetallic oxidative addition and escape-rebound pathways (see supporting information for computational details). 24 Owing to the extremely flat nature of the full catalyst potential energy surface (PES), our computations employed a model of the Fe catalyst in which some methyl groups replaced some phenyl groups.…”

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confidence: 99%

Iron Pincer Complexes as Catalysts and Intermediates in Alkyl–Aryl Kumada Coupling Reactions

et al. 2014

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Abstract. Iron-catalyzed alkyl-aryl Kumada coupling has developed into an efficient synthetic method, yet its mechanism remains vague. Here, we apply a bisoxazolinylphenylamido pincer ligand (Bopa) to stabilize the catalytically active Fe center, resulting in isolation and characterization of well-defined iron complexes whose catalytic roles are probed and confirmed. Reactivity studies of the iron complexes identifies an Fe(II) "ate" complex, [Fe(Bopa-Ph)(Ph) 2 ] -, as the active species for the oxidative addition of alkyl halide. Experiments using radicalprobe substrates and DFT computations reveal a bimetallic and radical mechanism for the oxidative addition. The kinetics of the coupling of an alkyl iodide with PhMgCl indicates that formation of the "ate" complex, rather than oxidative addition, is the turnover determining step. This work provides insights in iron-catalyzed cross coupling reactions of alkyl halides.3

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“…Hyperconjugation affects bond lengths, bond angles, and charge density distribution on carbons and hydrogens [12, 13]. The norbornene’s concave endo- face is well positioned for through spaces a-a* hyperconjugative interactions (Fig.…”

Section: Resultsmentioning

confidence: 99%

Visualization of Hyperconjugation and Subsequent Structural Distortions through 3D Printing of Crystal Structures

Mithila

Oyola‐Reynoso

Thuo

et al. 2016

LOC

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Background Structural distortions due to hyperconjugation in organic molecules, like norbornenes, are well captured through X-ray crystallographic data, but are sometimes difficult to visualize especially for those applying chemical knowledge and are not chemists. Methods Crystal structure from the Cambridge database were downloaded and converted to .stl format. The structures were then printed at the desired scale using a 3D printer. Results Replicas of the crystal structures were accurately reproduced in scale and any resulting distortions were clearly visible from the macroscale models. Through space interactions or effect of through space hyperconjugation was illustrated through loss of symmetry or distortions thereof. Conclusion The norbornene structures exhibits distortion that cannot be observed through conventional ball and stick modelling kits. We show that 3D printed models derived from crystallographic data capture even subtle distortions in molecules. We translate such crystallographic data into scaled-up models through 3D printing.

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The norbornene mystery revealed

Cited by 30 publications

References 26 publications

Molecular Docking via Olefinic OH···π Interactions: A Bulky Alkene Model System and Its Cooperativity

Molecular Docking via Olefinic OH···π Interactions: A Bulky Alkene Model System and Its Cooperativity

Iron Pincer Complexes as Catalysts and Intermediates in Alkyl–Aryl Kumada Coupling Reactions

Visualization of Hyperconjugation and Subsequent Structural Distortions through 3D Printing of Crystal Structures

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