Multiple Spin Scenarios in Transition‐Metal Complexes Involving Redox Non‐Innocent Ligands

Heims, Florian; Ray, Kallol

doi:10.1002/9781118898277.ch11

Cited by 2 publications

(1 citation statement)

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“…Transition-metal complexes containing redox-active, proradical ligands have long been attracting the researcher’s attention because the distribution of electrons between the metal centers and such ligands provides unique electronic properties [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ]. Extensive research has shown that the interplay of redox-active transition metal ions and pro-radical ligands plays an important role in biochemistry [ 11 , 12 , 13 ], with copper-containing enzymes being a prominent example [ 14 , 15 , 16 ]. For the copper complexes with catecholate ligands, which are an intermediate in the catalytic oxidation of catechols [ 17 , 18 ], the formation of semiquinonato copper complexes is a crucial step.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes

Ziółkowska

Witwicki

2023

IJMS

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The exchange coupling, represented by the J parameter, is of tremendous importance in understanding the reactivity and magnetic behavior of open-shell molecular systems. In the past, it was the subject of theoretical investigations, but these studies are mostly limited to the interaction between metallic centers. The exchange coupling between paramagnetic metal ions and radical ligands has hitherto received scant attention in theoretical studies, and thus the understanding of the factors governing this interaction is lacking. In this paper, we use DFT, CASSCF, CASSCF/NEVPT2, and DDCI3 methods to provide insight into exchange interaction in semiquinonato copper(II) complexes. Our primary objective is to identify structural features that affect this magnetic interaction. We demonstrate that the magnetic character of Cu(II)-semiquinone complexes are mainly determined by the relative position of the semiquinone ligand to the Cu(II) ion. The results can support the experimental interpretation of magnetic data for similar systems and can be used for the in-silico design of magnetic complexes with radical ligands.

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Section: Introductionmentioning

confidence: 99%

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes

Ziółkowska

Witwicki

2023

IJMS

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Copper‐Catalyzed Aziridination with Redox‐Active Ligands: Molecular Spin Catalysis

Ren

Cheaib

Jacquet

et al. 2018

Chemistry A European J

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Small-molecule catalysts as mimics of biological systems illustrate the chemists' attempts at emulating the tantalizing abilities displayed by nature's metalloenzymes. Among these innate behaviors, spin multistate reactivity is used by biological systems as it offers thermodynamic leverage towards challenging chemical reactivity but this concept is difficult to translate into the realm of synthetic organometallic catalysis. Here, we report a rare example of molecular spin catalysis involving multistate reactivity in a small-molecule biomimetic copper catalyst applied to aziridination. This behavior is supported by spin state flexibility enabled by the redox-active ligand.

show abstract

Multiple Spin Scenarios in Transition‐Metal Complexes Involving Redox Non‐Innocent Ligands

Cited by 2 publications

References 100 publications

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes

Copper‐Catalyzed Aziridination with Redox‐Active Ligands: Molecular Spin Catalysis

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