Data of: Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes
J. Musso, M. Benedikter, D. Wang, W. Frey, H. Altmann, and M. Buchmeiser. Dataset, (2021)Related to: J. V. Musso, M. J. Benedikter, D. Wang, W. Frey, H. J. Altmann, M. R. Buchmeiser, Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes Chem. Eur. J. 2020, 26, 8709. doi: 10.1002/chem.202000840.
DOI: 10.18419/darus-1715
Abstract
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.
Related to: J. V. Musso, M. J. Benedikter, D. Wang, W. Frey, H. J. Altmann, M. R. Buchmeiser, Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes Chem. Eur. J. 2020, 26, 8709. doi: 10.1002/chem.202000840
%0 Generic
%1 musso2021reversible
%A Musso, Janis
%A Benedikter, Mathis
%A Wang, Dongren
%A Frey, Wolfgang
%A Altmann, Hagen J.
%A Buchmeiser, Michael
%D 2021
%K darus mult ubs_10003 ubs_10018 ubs_20003 ubs_20023 ubs_30034 ubs_30036 ubs_30203 ubs_40064 unibibliografie
%R 10.18419/darus-1715
%T Data of: Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes
%X 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.
@misc{musso2021reversible,
abstract = {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.},
added-at = {2022-03-08T18:43:13.000+0100},
affiliation = {Musso, Janis/Universität Stuttgart, Benedikter, Mathis/Universität Stuttgart, Wang, Dongren/Universität Stuttgart, Frey, Wolfgang/Universität Stuttgart, Altmann, Hagen J./Universität Stuttgart, Buchmeiser, Michael/Universität Stuttgart},
author = {Musso, Janis and Benedikter, Mathis and Wang, Dongren and Frey, Wolfgang and Altmann, Hagen J. and Buchmeiser, Michael},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/27fa96bb3089840b1e88f6a9970fcdcee/unibiblio},
doi = {10.18419/darus-1715},
howpublished = {Dataset},
interhash = {50d89b5efaf667a67b12a9857343b79c},
intrahash = {7fa96bb3089840b1e88f6a9970fcdcee},
keywords = {darus mult ubs_10003 ubs_10018 ubs_20003 ubs_20023 ubs_30034 ubs_30036 ubs_30203 ubs_40064 unibibliografie},
note = {Related to: J. V. Musso, M. J. Benedikter, D. Wang, W. Frey, H. J. Altmann, M. R. Buchmeiser, Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes Chem. Eur. J. 2020, 26, 8709. doi: 10.1002/chem.202000840},
orcid-numbers = {Musso, Janis/0000-0002-8714-4511, Benedikter, Mathis/0000-0001-5711-6846, Frey, Wolfgang/0000-0002-6522-4190, Altmann, Hagen J./0000-0001-6832-6857, Buchmeiser, Michael/0000-0001-6472-5156},
timestamp = {2022-06-02T07:42:05.000+0200},
title = {Data of: Reversible N-Heterocyclic Carbene-Induced α-H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes},
year = 2021
}