HFEPR and Computational Studies on the Electronic Structure of a High-Spin Oxidoiron(IV) Complex in Solution

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L2)–, (L = N(Dipp)SiMe3), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me3Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.

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Imido Cobalt Complexes with Imidyl Character

10.26434/chemrxiv.14128709 ◽

2021 ◽

Author(s):

alexander Reckziegel ◽

Manjinder Kour ◽

Beatrice Battistella ◽

Stefan Mebs ◽

Katrin Beuthert ◽

...

Keyword(s):

Electronic Structure ◽

Spin Density ◽

High Spin ◽

Bond Activation ◽

High Spin State ◽

Cobalt Complexes ◽

Spectroscopic Methods ◽

Computational Studies ◽

Ancillary Ligand ◽

Unpaired Spin

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L2)–, (L = N(Dipp)SiMe3), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me3Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.

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Computational Studies of the Geometry and Electronic Structure of an All-Inorganic and Homogeneous Tetra-Ru-Polyoxotungstate Catalyst for Water Oxidation and Its Four Subsequent One-Electron Oxidized Forms

The Journal of Physical Chemistry A ◽

10.1021/jp907471h ◽

2010 ◽

Vol 114 (1) ◽

pp. 535-542 ◽

Cited By ~ 29

Author(s):

David Quiñonero ◽

Alexey L. Kaledin ◽

Aleksey E. Kuznetsov ◽

Yurii V. Geletii ◽

Claire Besson ◽

...

Keyword(s):

Electronic Structure ◽

Water Oxidation ◽

Computational Studies

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Theory Of 3d Transition Metal Defects In 3C SiC

MRS Proceedings ◽

10.1557/proc-442-637 ◽

1996 ◽

Vol 442 ◽

Author(s):

Harald Overhof

Keyword(s):

Electronic Structure ◽

Transition Metal ◽

Electronic Properties ◽

Crystal Field ◽

High Spin ◽

Crystal Field Splitting ◽

Large Crystal ◽

Field Splitting ◽

Vacancy Model ◽

The Difference

AbstractThe electronic properties of 3d transition metal (TM) defects located on one of the four different tetrahedral positions in 3C SiC are shown to be quite site-dependent. We explain the differences for the 3d TMs on the two substitutional sites within the vacancy model: the difference of the electronic structure between the carbon vacancy VC and the silicon vacancy VSi is responsible for the differences of the 3d TMs. The electronic properties of 3d TMs on the two tetrahedral interstitial sites differ even more: the TMs surrounded tetrahedrally by four Si atoms experience a large crystal field splitting while the tetrahedral C environment does not give rise to a significant crystal field splitting at all. It is only in the latter case that high-spin configurations are predicted.

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