Data of: Reversible N‐Heterocyclic Carbene‐Induced α‐H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes

DOI

The first reversible N‐heterocyclic carbene (NHC) induced α‐H abstraction in tungsten(VI) imido‐dialkyl dialkoxide complexes is reported. 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. 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.

Identifier
DOI https://doi.org/10.18419/darus-1715
Related Identifier https://doi.org/10.1002/chem.202000840
Metadata Access https://darus.uni-stuttgart.de/oai?verb=GetRecord&metadataPrefix=oai_datacite&identifier=doi:10.18419/darus-1715
Provenance
Creator Musso, Janis ORCID logo; Benedikter, Mathis ORCID logo; Wang, Dongren; Frey, Wolfgang ORCID logo; Altmann, Hagen J. ORCID logo; Buchmeiser, Michael ORCID logo
Publisher DaRUS
Contributor Buchmeiser, Michael
Publication Year 2021
Funding Reference Deutsche Forschungsgemeinschaft DFG BU2174/22‐1 ; Deutsche Forschungsgemeinschaft DFG 358283783‐CRC 1333
Rights CC BY 4.0; info:eu-repo/semantics/openAccess; http://creativecommons.org/licenses/by/4.0
OpenAccess true
Contact Buchmeiser, Michael (Universität Stuttgart)
Representation
Resource Type Dataset
Format application/zip
Size 343517704; 21041479
Version 1.0
Discipline Chemistry; Natural Sciences