Data · dataset · 2021
Data of: Reversible N‐Heterocyclic Carbene‐Induced α‐H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes
Listed in DaRUS
The first reversible N‐heterocyclic carbene (NHC) induced α‐H abstraction in tungsten(VI) imido‐dialkyl dialkoxide complexes is reported.
Description
Treatment of W(NAr)(CH2Ph)2(OtBu)2 (Ar=2,6‐dichlorophenyl, 2,6‐dimethylphenyl, 2,6‐diisopropylphenyl) with different NHCs leads to the formation of complexes of the type W(NAr)(CHPh)(NHC)(CH2Ph)(OtBu) in excellent isolated yields of up to 96 %. The highly unusual release of the tert‐butoxide ligand as tBuOH in the course of the reaction was observed.
The formed alkylidene complexes and tBuOH are in an equilibrium with the NHC and the dialkyl complexes. Reaction kinetics were monitored by 1H NMR spectroscopy. A correlation between the steric and electronic properties of the NHC and the reaction rates was observed.
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Kinetics of a deuterium‐labeled complex in comparison to its non‐deuterated counterpart revealed the presence of a strong primary kinetic isotope effect (KIE) of 4.2, indicating that α‐H abstraction is the rate‐determining step (RDS) of the reaction. All primary data files and processed data of the original journal article can be found here. Procedures, recation conditions and used analytical equipment is discussed in detail in the supporting information of the paper.
NMR Spectra as well as kinetics data are named according to the numbering in the publication. 1H-NMR and 13C-NMR spectra were recorded using a Bruker Avance III 400 (400MHzfor 1H, 101MHz for 13C) spectrometer.
Links
Where it is published
- Dataverse dataset page darus.uni-stuttgart.de/dataset.xhtml?persistentId=doi%3A10.18419%2FDARUS-1715 ↗
landing page · from darus uni stuttgart de
- DOI doi.org/10.18419/darus-1715 ↗
DOI / persistent id · from darus uni stuttgart de
Catalogue records · 1
- Dataverse API darus.uni-stuttgart.de/api/datasets/:persistentId/?persistentId=doi%3A10.18419%2FDARU… ↗
metadata API · from darus uni stuttgart de
Topics
- Stated by source
- Chemistry
- From keywords
- Chemistry
- Inferred from text
- Organic chemistry 70%
Provenance · 1 source records, 9 field assertions
| Source | Key | Last seen | Raw |
|---|---|---|---|
| DaRUS | doi:10.18419/DARUS-1715 | 12 d ago | JSON v1 |
| Field | Assertion | Extractor | Evidence |
|---|---|---|---|
| concepts[field].anzsrc:group:3405 | enrichment · darus uni stuttgart de | taxonomy-embedding@1.1.0 | title+keywords+description (70%) |
| concepts[field].dataverse_subject:chemistry | source · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 | /subjects |
| concepts[field].local:field:chemistry | mapping · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 | /subjects |
| created_date | source · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 | |
| description | source · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 | /description |
| publication_date | source · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 | |
| title | source · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 | /name |
| updated_date | source · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 | |
| version_label | source · darus uni stuttgart de | connector:darus_uni_stuttgart_de@1.0.0 |