On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes

M. Heckenroth, A. Neels, M.G. Garnier, P. Aebi, A.W. Ehlers, M. Albrecht

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Sterically similar palladium dicarbene complexes have been synthesized that comprise permethylated dicarbene ligands which bind the metal center either in a normal coordination mode via C2 or abnormally via C4. Due to the strong structural analogy of the complexes, differences in reactivity patterns may be attributed to the distinct electronic impact of normal versus abnormal carbene bonding, while stereoelectronic effects are negligible. Unique reactivity patterns have been identified for the abnormal carbene complexes, specifically upon reaction with Lewis acids and in oxidative addition-reductive elimination sequences. These reactivities as well as analytical investigations using X-ray diffraction and X-ray photoelectron spectros-copy indicate that the C4 bonding mode increases the electron density at the metal center substantially, classifying such C4-bound carbene ligands amongst the most basic neutral donors known thus far. A direct application of this enhanced electron density at the metal center is demonstrated by the catalytic H
Original languageEnglish
Pages (from-to)9375-86
JournalChemistry: A European Journal
Volume15
Issue number37
DOIs
Publication statusPublished - 2009

Fingerprint

Metals
Carrier concentration
Ligands
Lewis Acids
Palladium
Photoelectrons
X ray diffraction
X rays
Acids
carbene

Cite this

Heckenroth, M., Neels, A., Garnier, M. G., Aebi, P., Ehlers, A. W., & Albrecht, M. (2009). On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes. Chemistry: A European Journal, 15(37), 9375-86. https://doi.org/10.1002/chem.200900249
Heckenroth, M. ; Neels, A. ; Garnier, M.G. ; Aebi, P. ; Ehlers, A.W. ; Albrecht, M. / On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes. In: Chemistry: A European Journal. 2009 ; Vol. 15, No. 37. pp. 9375-86.
@article{61f847b6d8ba49fcbc84ac3a4691348c,
title = "On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes",
abstract = "Sterically similar palladium dicarbene complexes have been synthesized that comprise permethylated dicarbene ligands which bind the metal center either in a normal coordination mode via C2 or abnormally via C4. Due to the strong structural analogy of the complexes, differences in reactivity patterns may be attributed to the distinct electronic impact of normal versus abnormal carbene bonding, while stereoelectronic effects are negligible. Unique reactivity patterns have been identified for the abnormal carbene complexes, specifically upon reaction with Lewis acids and in oxidative addition-reductive elimination sequences. These reactivities as well as analytical investigations using X-ray diffraction and X-ray photoelectron spectros-copy indicate that the C4 bonding mode increases the electron density at the metal center substantially, classifying such C4-bound carbene ligands amongst the most basic neutral donors known thus far. A direct application of this enhanced electron density at the metal center is demonstrated by the catalytic H",
author = "M. Heckenroth and A. Neels and M.G. Garnier and P. Aebi and A.W. Ehlers and M. Albrecht",
year = "2009",
doi = "10.1002/chem.200900249",
language = "English",
volume = "15",
pages = "9375--86",
journal = "Chemistry: A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "37",

}

Heckenroth, M, Neels, A, Garnier, MG, Aebi, P, Ehlers, AW & Albrecht, M 2009, 'On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes' Chemistry: A European Journal, vol. 15, no. 37, pp. 9375-86. https://doi.org/10.1002/chem.200900249

On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes. / Heckenroth, M.; Neels, A.; Garnier, M.G.; Aebi, P.; Ehlers, A.W.; Albrecht, M.

In: Chemistry: A European Journal, Vol. 15, No. 37, 2009, p. 9375-86.

Research output: Contribution to JournalArticleAcademicpeer-review

TY - JOUR

T1 - On the electronic impact of abnormal C4-bonding in N-heterocyclic carbene complexes

AU - Heckenroth, M.

AU - Neels, A.

AU - Garnier, M.G.

AU - Aebi, P.

AU - Ehlers, A.W.

AU - Albrecht, M.

PY - 2009

Y1 - 2009

N2 - Sterically similar palladium dicarbene complexes have been synthesized that comprise permethylated dicarbene ligands which bind the metal center either in a normal coordination mode via C2 or abnormally via C4. Due to the strong structural analogy of the complexes, differences in reactivity patterns may be attributed to the distinct electronic impact of normal versus abnormal carbene bonding, while stereoelectronic effects are negligible. Unique reactivity patterns have been identified for the abnormal carbene complexes, specifically upon reaction with Lewis acids and in oxidative addition-reductive elimination sequences. These reactivities as well as analytical investigations using X-ray diffraction and X-ray photoelectron spectros-copy indicate that the C4 bonding mode increases the electron density at the metal center substantially, classifying such C4-bound carbene ligands amongst the most basic neutral donors known thus far. A direct application of this enhanced electron density at the metal center is demonstrated by the catalytic H

AB - Sterically similar palladium dicarbene complexes have been synthesized that comprise permethylated dicarbene ligands which bind the metal center either in a normal coordination mode via C2 or abnormally via C4. Due to the strong structural analogy of the complexes, differences in reactivity patterns may be attributed to the distinct electronic impact of normal versus abnormal carbene bonding, while stereoelectronic effects are negligible. Unique reactivity patterns have been identified for the abnormal carbene complexes, specifically upon reaction with Lewis acids and in oxidative addition-reductive elimination sequences. These reactivities as well as analytical investigations using X-ray diffraction and X-ray photoelectron spectros-copy indicate that the C4 bonding mode increases the electron density at the metal center substantially, classifying such C4-bound carbene ligands amongst the most basic neutral donors known thus far. A direct application of this enhanced electron density at the metal center is demonstrated by the catalytic H

U2 - 10.1002/chem.200900249

DO - 10.1002/chem.200900249

M3 - Article

VL - 15

SP - 9375

EP - 9386

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

SN - 0947-6539

IS - 37

ER -