Replacement of N-heterocyclic carbenes by N-heterocyclic silylenes at a Pd(0) center: Experiment and theory

Alexander Zeller; Frank Bielert; Peter Haerter; Wolfgang A. Herrmann; Thomas Strassner

doi:10.1016/j.jorganchem.2005.03.061

Replacement of N-heterocyclic carbenes by N-heterocyclic silylenes at a Pd(0) center: Experiment and theory

Alexander Zeller, Frank Bielert, Peter Haerter, Wolfgang A. Herrmann, Thomas Strassner

Technical University of Munich

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

28 Scopus citations

Abstract

Via NMR-spectroscopy the relative reactivity of N-heterocyclic silylenes (NHSi) and carbenes (NHC) was studied. Reaction of sterically crowded bis-N-heterocyclic Pd(0) carbene complexes with free N-heterocyclic silylenes led to complete displacement of the N-heterocyclic carbene, which is unexpected knowing that usually a silylene is a weaker bound ligand compared to a carbene. High-level DFT calculations on a small model system and the experimentally used complexes confirm the experimental findings and indicate that steric interactions play an important role in the substitution reaction.

Original language	English
Pages (from-to)	3292-3299
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	690
Issue number	13
DOIs	https://doi.org/10.1016/j.jorganchem.2005.03.061
State	Published - 1 Jul 2005

Keywords

DFT calculations
N-Heterocyclic carbene
N-Heterocyclic silylene
Palladium
Steric repulsion

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10.1016/j.jorganchem.2005.03.061

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title = "Replacement of N-heterocyclic carbenes by N-heterocyclic silylenes at a Pd(0) center: Experiment and theory",

abstract = "Via NMR-spectroscopy the relative reactivity of N-heterocyclic silylenes (NHSi) and carbenes (NHC) was studied. Reaction of sterically crowded bis-N-heterocyclic Pd(0) carbene complexes with free N-heterocyclic silylenes led to complete displacement of the N-heterocyclic carbene, which is unexpected knowing that usually a silylene is a weaker bound ligand compared to a carbene. High-level DFT calculations on a small model system and the experimentally used complexes confirm the experimental findings and indicate that steric interactions play an important role in the substitution reaction.",

keywords = "DFT calculations, N-Heterocyclic carbene, N-Heterocyclic silylene, Palladium, Steric repulsion",

author = "Alexander Zeller and Frank Bielert and Peter Haerter and Herrmann, {Wolfgang A.} and Thomas Strassner",

note = "Funding Information: We are grateful to the Leibniz-Rechenzentrum Muenchen for providing computer time and financial support of the Fonds der Chemischen Industrie. We thank Dr. Christian Gst{\"o}ttmayr for helpful discussions. A.Z. thanks the “Gesellschaft der Freunde und F{\"o}rderer der Technischen Universit{\"a}t Dresden” for a generous travel grant.",

year = "2005",

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doi = "10.1016/j.jorganchem.2005.03.061",

language = "English",

volume = "690",

pages = "3292--3299",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

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T1 - Replacement of N-heterocyclic carbenes by N-heterocyclic silylenes at a Pd(0) center

T2 - Experiment and theory

AU - Zeller, Alexander

AU - Bielert, Frank

AU - Haerter, Peter

AU - Herrmann, Wolfgang A.

AU - Strassner, Thomas

N1 - Funding Information: We are grateful to the Leibniz-Rechenzentrum Muenchen for providing computer time and financial support of the Fonds der Chemischen Industrie. We thank Dr. Christian Gstöttmayr for helpful discussions. A.Z. thanks the “Gesellschaft der Freunde und Förderer der Technischen Universität Dresden” for a generous travel grant.

PY - 2005/7/1

Y1 - 2005/7/1

N2 - Via NMR-spectroscopy the relative reactivity of N-heterocyclic silylenes (NHSi) and carbenes (NHC) was studied. Reaction of sterically crowded bis-N-heterocyclic Pd(0) carbene complexes with free N-heterocyclic silylenes led to complete displacement of the N-heterocyclic carbene, which is unexpected knowing that usually a silylene is a weaker bound ligand compared to a carbene. High-level DFT calculations on a small model system and the experimentally used complexes confirm the experimental findings and indicate that steric interactions play an important role in the substitution reaction.

AB - Via NMR-spectroscopy the relative reactivity of N-heterocyclic silylenes (NHSi) and carbenes (NHC) was studied. Reaction of sterically crowded bis-N-heterocyclic Pd(0) carbene complexes with free N-heterocyclic silylenes led to complete displacement of the N-heterocyclic carbene, which is unexpected knowing that usually a silylene is a weaker bound ligand compared to a carbene. High-level DFT calculations on a small model system and the experimentally used complexes confirm the experimental findings and indicate that steric interactions play an important role in the substitution reaction.

KW - DFT calculations

KW - N-Heterocyclic carbene

KW - N-Heterocyclic silylene

KW - Palladium

KW - Steric repulsion

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U2 - 10.1016/j.jorganchem.2005.03.061

DO - 10.1016/j.jorganchem.2005.03.061

M3 - Article

AN - SCOPUS:20144374443

SN - 0022-328X

VL - 690

SP - 3292

EP - 3299

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 13

ER -

Replacement of N-heterocyclic carbenes by N-heterocyclic silylenes at a Pd(0) center: Experiment and theory

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Keywords

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