Organometallics
Article
moment of the oxygen nuclei and the electric field gradient (EFG)
arising at these sites, are calculated from the EFG tensor eigenvalues
V11, V22, and V33.
Swiss-Norwegian beamline, BM01B, at ESRF (proposal # 01-
01-905).
EXAFS. X-ray absorption spectra were acquired at the ESRF, using
the Swiss-Norwegian beamline BM01B (proposal # 01-01-905), at
room temperature at the tungsten LIII edge, with a double-crystal
Si(111) monochromator detuned 70% to reduce the higher harmonics
of the beam. The spectra were recorded in the transmission mode
between 9.98 and 11.45 keV. The supported W sample was packaged
within an argon-filled glovebox in a double airtight sample holder
equipped with Kapton windows. The spectra analyzed were the results
of four such acquisitions, and no evolution could be observed between
the first and last acquisition. The data analyses were performed by
standard procedures using in particular the program Athena60 and the
EXAFS fitting program RoundMidnigh”,61 from the MAX package,
using spherical waves. The program FEFF8 was used to calculate
theoretical files for phases and amplitudes based on model clusters of
atoms.62 The value of the scale factor, S02 = 0.94, was determined from
the k2 and k3χ(k) spectra of a reference compound, a sample of
[WO(CH2tBu)3Cl] complex diluted in BN and carefully mixed and
pressed as a pellet (one oxo at 1.70(1) Å, three carbon atoms at
2.10(1) Å, and one chlorine at 2.43(1) Å in the first coordination
sphere, with three carbon atoms at 3.28(3) Å).13 The refinements
were performed by fitting the structural parameters Ni, Ri, σi, and the
energy shift, ΔE0 (the same for all shells). The fit residue, ρ(%), was
calculated by the following formula:
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cal
ρ =
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ASSOCIATED CONTENT
* Supporting Information
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S
The Supporting Information is available free of charge on the
Additional details on DFT calculations and catalysis
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AUTHOR INFORMATION
Corresponding Authors
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was funded by the Agence Nationale de la Recherche
(ANR-12-BS07-0021-01, OXOCAT). CNRS, French Ministry
of Research and Higher Education, Institut de Chimie de Lyon,
́
Chevreul Institute (FR 2638), Region Nord−Pas de Calais,
FEDER, are acknowledged for their supplementary support.
Financial support from the TGE RMN THC Fr3050 for
conducting the high-field solid-state NMR is gratefully
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́ ́
acknowledged. We thank the HPCs CALcule, Midi-Pyrenees
(CALMIP-EOS, grant P0833), for the generous allocation of
computer time. We would also like to thank Hermann Emerich
for his help during the recording of the XAS spectra on the
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