Data of: Reversible N‐Heterocyclic Carbene‐Induced α‐H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes (ICPSR doi:10.18419/darus-1715)

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Document Description

Citation

Title:

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

Identification Number:

doi:10.18419/darus-1715

Distributor:

DaRUS

Date of Distribution:

2021-04-08

Version:

1

Bibliographic Citation:

Musso, Janis; Benedikter, Mathis; Wang, Dongren; Frey, Wolfgang; Altmann, Hagen J.; Buchmeiser, Michael, 2021, "Data of: Reversible N‐Heterocyclic Carbene‐Induced α‐H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes", https://doi.org/10.18419/darus-1715, DaRUS, V1

Study Description

Citation

Title:

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

Identification Number:

doi:10.18419/darus-1715

Authoring Entity:

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)

Grant Number:

BU2174/22‐1

Grant Number:

358283783‐CRC 1333

Distributor:

DaRUS

Access Authority:

Buchmeiser, Michael

Depositor:

Musso, Janis

Date of Deposit:

2021-03-12

Study Scope

Keywords:

Chemistry, Alpha-H-abstraction, tungsten-alkylidene

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.

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Sources Statement

Data Access

Notes:

CC BY Waiver

Other Study Description Materials

Related Publications

Citation

Identification Number:

10.1002/chem.202000840

Bibliographic Citation:

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.

Other Study-Related Materials

Label:

Kinetics Measurements.zip

Notes:

application/zip

Other Study-Related Materials

Label:

NMR Spectra.zip

Notes:

application/zip