scholarly journals Spectroscopic and Computational Studies of a Series of High-Spin Ni(II) Thiolate Complexes

2010 ◽  
Vol 49 (14) ◽  
pp. 6535-6544 ◽  
Author(s):  
Katherine M. Van Heuvelen ◽  
Jaeheung Cho ◽  
Timothy Dingee ◽  
Charles G. Riordan ◽  
Thomas C. Brunold
Keyword(s):  
High Spin ◽  
Computational Studies ◽  
Thiolate Complexes

scholarly journals Imido Cobalt Complexes with Imidyl Character

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)L<sub>2</sub>)<sup>–</sup>, (L = N(Dipp)SiMe<sub>3</sub>), 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 Me<sub>3</sub>Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.<br>

scholarly journals Imido Cobalt Complexes with Imidyl Character

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)L<sub>2</sub>)<sup>–</sup>, (L = N(Dipp)SiMe<sub>3</sub>), 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 Me<sub>3</sub>Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.<br>

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

2016 ◽  
Vol 55 (8) ◽  
pp. 3933-3945 ◽  
Author(s):  
Lukas Bucinsky ◽  
Gregory T. Rohde ◽  
Lawrence Que ◽  
Andrew Ozarowski ◽  
J. Krzystek ◽  
...  
Keyword(s):  
Electronic Structure ◽  
High Spin ◽  
Computational Studies

scholarly journals Unravelling the mechanism of cobalt-catalysed remote C–H nitration of 8-aminoquinolinamides and expansion of substrate scope towards 1-naphthylpicolinamide

2020 ◽  
Vol 11 (2) ◽  
pp. 534-542
Author(s):  
Melody Chu ◽  
Oriol Planas ◽  
Anna Company ◽  
Xavi Ribas ◽  
Alex Hamilton ◽  
...  
Keyword(s):  
High Spin ◽  
Computational Studies ◽  
Radical Coupling

Computational studies of the Co-catalyzed remote nitration of 8-aminoquinolinamides have found the mechanism to operate through an unexpected high-spin induced remote radical-coupling.

scholarly journals Structure and Reactivity of a High-Spin, Non-Heme Iron(III)-Superoxo Complex Supported by Phosphinimide Ligands

2021 ◽  
Author(s):  
Charles Winslow ◽  
Heui Beom Lee ◽  
Mackenzie J. Field ◽  
Simon J Teat ◽  
Jonathan Rittle
Keyword(s):  
Single Crystals ◽  
High Spin ◽  
Heme Iron ◽  
Computational Studies ◽  
Oxidation Processes ◽  
Transient Nature ◽  
Non Heme Iron ◽  
The Stability ◽  
Oxidation Chemistry ◽  
High Spin Iron

Non-heme iron oxygenases utilize dioxygen to accomplish challenging chemical oxidations. Further understanding of the Fe-O<sub>2</sub> intermediates implicated in these processes is challenged by their highly transient nature. To that end, we have developed a ligand platform featuring phosphinimide donors intended to stabilize oxidized, high-spin iron complexes. O<sub>2</sub> exposure of single crystals of a three-coordinate Fe(II) complex of this framework allowed for in crystallo trapping of a terminally-bound Fe-O<sub>2</sub> complex suitable for XRD characterization. Spectroscopic and computational studies of this species support a high-spin Fe(III) center antiferromagnetically coupled to a superoxide ligand, similar to that proposed for numerous non-heme iron oxygenases. In addition to the stability of this synthetic Fe-O<sub>2</sub> complex, its ability to engage in a range of stoichiometric and catalytic oxidation processes demonstrates that this iron-phosphinimide system is primed for development in modelling oxidizing bioinorganic intermediates and green oxidation chemistry.

scholarly journals Structure and Reactivity of a High-Spin, Non-Heme Iron(III)-Superoxo Complex Supported by Phosphinimide Ligands

2021 ◽  
Author(s):  
Charles Winslow ◽  
Heui Beom Lee ◽  
Mackenzie J. Field ◽  
Simon J Teat ◽  
Jonathan Rittle
Keyword(s):  
Single Crystals ◽  
High Spin ◽  
Heme Iron ◽  
Computational Studies ◽  
Oxidation Processes ◽  
Transient Nature ◽  
Non Heme Iron ◽  
The Stability ◽  
Oxidation Chemistry ◽  
High Spin Iron

Non-heme iron oxygenases utilize dioxygen to accomplish challenging chemical oxidations. Further understanding of the Fe-O<sub>2</sub> intermediates implicated in these processes is challenged by their highly transient nature. To that end, we have developed a ligand platform featuring phosphinimide donors intended to stabilize oxidized, high-spin iron complexes. O<sub>2</sub> exposure of single crystals of a three-coordinate Fe(II) complex of this framework allowed for in crystallo trapping of a terminally-bound Fe-O<sub>2</sub> complex suitable for XRD characterization. Spectroscopic and computational studies of this species support a high-spin Fe(III) center antiferromagnetically coupled to a superoxide ligand, similar to that proposed for numerous non-heme iron oxygenases. In addition to the stability of this synthetic Fe-O<sub>2</sub> complex, its ability to engage in a range of stoichiometric and catalytic oxidation processes demonstrates that this iron-phosphinimide system is primed for development in modelling oxidizing bioinorganic intermediates and green oxidation chemistry.

Ligand Oxidations in High-Spin Nickel Thiolate Complexes and Zinc Analogues

2004 ◽  
Vol 43 (24) ◽  
pp. 7726-7734 ◽  
Author(s):  
Balwant S. Chohan ◽  
Steven C. Shoner ◽  
Julie A. Kovacs ◽  
Michael J. Maroney
Keyword(s):  
High Spin ◽  
Thiolate Complexes

Evidence for high-spin-to-low-spin transition under pressure in Fe 72 Pt 28 Invar alloy

2000 ◽  
Vol 80 (2) ◽  
pp. 155-163 ◽  
Author(s):  
S. Odin, F. Baudelet, E. Dartyge, J. P
Keyword(s):  
High Spin ◽  
Spin Transition ◽  
Invar Alloy
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