Redox-Active Ligand-Mediated Oxidative Addition and Reductive Elimination at Square Planar Cobalt(III): Multielectron Reactions for Cross-Coupling

Alkyl–alkyl cross coupling through well-defined mechanisms that allow for controlled oxidative addition, prevent beta-hydride elimination, and tolerate hindered electrophiles are still challenging. We describe the first report of a redox-active ligand-enabled alkyl–alkyl cross coupling using a d0 metal. This (tris)amido ScIII complex as well as the oxidized variant are thor-oughly characterized (NMR, X-ray, EPR, CV, UV-Vis, DFT). Insight into the likely radical nature of the mechanism is dis-closed. Additionally, a substrate scope that includes functional groups incompatible with late transition metal catalysis, and both coupling partners bearing beta-hydrogens is reported.

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Molecular and electronic structure of square-planar nickel(ii), nickel(iii) and nickel(iii)π-cation radical complexes with a tetradentate o-phenylenedioxamidate redox-active ligand

Dalton Transactions ◽

10.1039/b502481a ◽

2005 ◽

pp. 2527 ◽

Cited By ~ 32

Author(s):

Rosa Carrasco ◽

Joan Cano ◽

Xavier Ottenwaelder ◽

Ally Aukauloo ◽

Yves Journaux ◽

...

Keyword(s):

Electronic Structure ◽

Cation Radical ◽

Redox Active Ligand ◽

Active Ligand ◽

Redox Active ◽

Square Planar ◽

Molecular And Electronic Structure

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Redox-active ligand-mediated Co–Cl bond-forming reactions at reducing square planar cobalt(III) centers

Polyhedron ◽

10.1016/j.poly.2009.06.046 ◽

2010 ◽

Vol 29 (1) ◽

pp. 164-169 ◽

Cited By ~ 57

Author(s):

Aubrey L. Smith ◽

Laura A. Clapp ◽

Kenneth I. Hardcastle ◽

Jake D. Soper

Keyword(s):

Bond Forming ◽

Redox Active Ligand ◽

Active Ligand ◽

Redox Active ◽

Square Planar ◽

Bond Forming Reactions

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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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