Mechanism of Redox-Active Ligand-Assisted Nitrene-Group Transfer in a ZrIVComplex: Direct Ligand-to-Ligand Charge Transfer Preferred

<div>Metalloenzymes use earth-abundant non-noble metals to perform</div><div>high‐fidelity transformations in the biological world. To ensure chemical efficiency, metalloenzymes have acquired evolutionary reactivity‐enhancing tools. Among these, the entatic state model states that a strong steric entatic state, strongly improving the reactivity. However, while the original definition refers both to the transfer of electrons or chemical groups, the chemical application of this concept in synthetic systems has mostly focused on electron transfer, therefore eluding chemical transformations. Here we report that a highly‐strained redox-active ligand enables a cooper complex to perform catalytic nitrogen- and carbon-‐group transfer in as fast as two minutes, thus exhibiting a strong increase in reactivity compared to its unstrained analogue. This is the first report combining two reactivity-‐enhancing features from metalloenzymes, entasis and redox cofactors, applied to group-transfer catalysis.<br></div>

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Optimizing Group Transfer Catalysis by Copper Complex with Redox-Active Ligand in an Entatic State

iScience ◽

10.1016/j.isci.2020.100955 ◽

2020 ◽

Vol 23 (3) ◽

pp. 100955 ◽

Cited By ~ 3

Author(s):

Yufeng Ren ◽

Jeremy Forté ◽

Khaled Cheaib ◽

Nicolas Vanthuyne ◽

Louis Fensterbank ◽

...

Keyword(s):

Copper Complex ◽

Group Transfer ◽

Redox Active Ligand ◽

Entatic State ◽

Active Ligand ◽

Redox Active

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High-Performance Group Transfer Catalysis by Copper Complex with Redox-Active Ligand in an Entatic State

10.26434/chemrxiv.8965475.v1 ◽

2019 ◽

Author(s):

Yufeng Ren ◽

Jeremy Forte ◽

Khaled Cheaib ◽

Nicolas Vanthuyne ◽

Louis Fensterbank ◽

...

Keyword(s):

Noble Metals ◽

Strong Increase ◽

Chemical Transformations ◽

Chemical Application ◽

Group Transfer ◽

Redox Active Ligand ◽

Entatic State ◽

Active Ligand ◽

Redox Active ◽

Original Definition

<div>Metalloenzymes use earth-abundant non-noble metals to perform</div><div>high‐fidelity transformations in the biological world. To ensure chemical efficiency, metalloenzymes have acquired evolutionary reactivity‐enhancing tools. Among these, the entatic state model states that a strong steric entatic state, strongly improving the reactivity. However, while the original definition refers both to the transfer of electrons or chemical groups, the chemical application of this concept in synthetic systems has mostly focused on electron transfer, therefore eluding chemical transformations. Here we report that a highly‐strained redox-active ligand enables a cooper complex to perform catalytic nitrogen- and carbon-‐group transfer in as fast as two minutes, thus exhibiting a strong increase in reactivity compared to its unstrained analogue. This is the first report combining two reactivity-‐enhancing features from metalloenzymes, entasis and redox cofactors, applied to group-transfer catalysis.<br></div>

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Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione

Organometallics ◽

10.1021/acs.organomet.9b00611 ◽

2019 ◽

Vol 39 (1) ◽

pp. 66-73 ◽

Cited By ~ 1

Author(s):

Vladimir G. Sokolov ◽

Tatyana S. Koptseva ◽

Roman V. Rumyantcev ◽

Xiao-Juan Yang ◽

Yanxia Zhao ◽

...

Keyword(s):

Redox Active Ligand ◽

Active Ligand ◽

Redox Active ◽

Aluminum Complexes

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POSSIBILITY OF MOLECULAR-SWITCH WITH CONTROLLED HYDROGEN BOND: UTILITY OF COMBINATION OF 2,2′-BIIMIDAZOLE AND REDOX-ACTIVE LIGAND

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633605001477 ◽

2005 ◽

Vol 04 (01) ◽

pp. 333-344 ◽

Cited By ~ 3

Author(s):

HIROTOSHI MORI ◽

EISAKU MIYOSHI

Keyword(s):

Density Functional ◽

Molecular Level ◽

Molecular Switch ◽

Vibration Band ◽

Functional Theory ◽

Inorganic Molecule ◽

Redox Active Ligand ◽

Active Ligand ◽

Redox Active ◽

Stretching Vibration

A new inorganic molecule [ Co(Hbim) ( C 6 H 4 O 2)( NH 3)2]2 that can be used as a new optically durable molecular switch was theoretically designed in the framework of density functional theory. Three stable minima, belonging to 1 A g , 5 A 1, and 9 A g states, were found in the complex. Theoretically predicted infrared spectra of the complexes showed that a strong peak of NH stretching vibration is observed at 2690, 2120, and 2770 cm -1 in the 1 A g , 5 A 1, and 9 A g states, respectively. The apparent red shift of the NH stretching vibration band in the 5 A 1 state make it possible to distinguish the electronic state from others (1 A g and 9 A g ). This means that the complex can be used as a molecular level switch whose memory can be stably read by IR light without any photoreaction process; namely, without memory degradation.

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Isolation of a uranium(iii) benzophenone ketyl radical that displays redox-active ligand behaviour

Dalton Transactions ◽

10.1039/c4dt01636j ◽

2014 ◽

Vol 43 (48) ◽

pp. 17885-17888 ◽

Cited By ~ 20

Author(s):

Ellen M. Matson ◽

John J. Kiernicki ◽

Nickolas H. Anderson ◽

Phillip E. Fanwick ◽

Suzanne C. Bart

Keyword(s):

Ketyl Radical ◽

Radical Complex ◽

Redox Active Ligand ◽

Active Ligand ◽

Redox Active ◽

Reducing Equivalents

The first uranium(iii) charge separated ketyl radical complex, Tp*2U(OC·Ph2), has been isolated and acts as a potent two-electron reductant with reducing equivalents derived from both uranium and the redox-active benzophenone.

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