scholarly journals Metal–Ligand Bifunctional Catalysis: The “Accepted” Mechanism, the Issue of Concertedness, and the Function of the Ligand in Catalytic Cycles Involving Hydrogen Atoms

ACS Catalysis ◽  
2017 ◽  
Vol 7 (10) ◽  
pp. 6635-6655 ◽  
Author(s):  
Pavel A. Dub ◽  
John C. Gordon
Keyword(s):  
Bifunctional Catalysis ◽  
Hydrogen Atoms ◽  
Catalytic Cycles ◽  
Metal Ligand

ChemInform Abstract: Asymmetric Hydrogenation Through Metal-Ligand Bifunctional Catalysis

ChemInform ◽  
2008 ◽  
Vol 39 (3) ◽  
Author(s):  
Ryoji Noyori ◽  
Takeshi Ohkuma ◽  
Christian A. Sandoval ◽  
Kilian Muniz
Keyword(s):  
Asymmetric Hydrogenation ◽  
Bifunctional Catalysis ◽  
Metal Ligand

Ligand Field-Actuated Non-Innocence of Acetylacetonate

2020 ◽  
Author(s):  
Morten Gotthold Vinum ◽  
Laura Voigt ◽  
Steen Hansen ◽  
Colby Bell ◽  
Kensha Marie Clark ◽  
...  
Keyword(s):  
Noble Metals ◽  
Chemical Reactivity ◽  
Energy Levels ◽  
Orbital Energy ◽  
Ligand Field ◽  
Ligand Orbital ◽  
Catalytic Cycles ◽  
Electrochemical Potentials ◽  
New Strategies ◽  
Metal Ligand

<p>The quest for simple ligands to participate in concerted base metal-ligand multiple-electron redox events is driven by perspectives of replacing noble metals in catalysis and for discovering novel chemical reactivity. Yet the vast majority of simple ligand systems displays electrochemical potentials impractical for catalytic cycles substantiating the importance of new strategies towards aligned metal–ligand orbital energy levels. We herein demonstrate the possibility to establish and tame the elusive <i>non-innocence</i> of the ubiquitous acetylacetonate (acac), that is the most commonly employed anionic, chelating ligand towards elements across the entire Periodic Table. By employing the ligand field in the high-spin Cr(II) as a thermodynamic switch, we were able to chemically tailor the occurrence of metal–ligand redox events. The very mechanism can be understood as a destabilization of the d<i><sub>z</sub></i>2 orbital relative to the <i>pi</i>* LUMO of acac, which proffers a generalizable strategy to synthetically engineer non-innocence with seemingly redox-inactive ligands. </p>

ChemInform Abstract: Asymmetric Hydrogenation Through Metal-Ligand Bifunctional Catalysis

ChemInform ◽  
2010 ◽  
Vol 41 (38) ◽  
pp. no-no
Author(s):  
Ryoji Noyori ◽  
Takeshi Ohkuma ◽  
Christian A. Sandoval ◽  
Kilian Muniz
Keyword(s):  
Asymmetric Hydrogenation ◽  
Bifunctional Catalysis ◽  
Metal Ligand

Metal–ligand bifunctional catalysis for asymmetric hydrogenation

2005 ◽  
Vol 363 (1829) ◽  
pp. 901-912 ◽  
Author(s):  
Ryoji Noyori ◽  
Christian A Sandoval ◽  
Kilian Muñiz ◽  
Takeshi Ohkuma
Keyword(s):  
Asymmetric Catalysis ◽  
Asymmetric Hydrogenation ◽  
Enantioselective Hydrogenation ◽  
Molecular Surface ◽  
Metal Alkoxide ◽  
Bifunctional Catalysis ◽  
Bifunctional Mechanism ◽  
Prochiral Ketones ◽  
Membered Transition State ◽  
Metal Ligand

Chiral diphosphine/1,2-diamine–Ru(II) complexes catalyse the rapid, productive and enantioselective hydrogenation of simple ketones. The carbonyl-selective hydrogenation takes place via a non-classical metal–ligand bifunctional mechanism. The reduction of the C=O function occurs in the outer coordination sphere of an 18e trans -RuH 2 (diphosphine)(diamine) complex without interaction between the unsaturated moiety and the metallic centre. The Ru atom donates a hydride and the NH 2 ligand delivers a proton through a pericyclic six-membered transition state, directly giving an alcoholic product without metal alkoxide formation. The enantiofaces of prochiral ketones are differentiated on the chiral molecular surface of the saturated RuH 2 species. This asymmetric catalysis manifests the significance of ‘kinetic’ supramolecular chemistry.

Metal—Ligand Bifunctional Catalysis for Asymmetric Hydrogenation

ChemInform ◽  
2006 ◽  
Vol 37 (24) ◽  
Author(s):  
Ryoji Noyori ◽  
Christian A. Sandoval ◽  
Kilian Muniz ◽  
Takeshi Ohkuma
Keyword(s):  
Asymmetric Hydrogenation ◽  
Bifunctional Catalysis ◽  
Metal Ligand

scholarly journals Aromaticity in catalysis: metal ligand cooperation via ligand dearomatization and rearomatization

2021 ◽  
Author(s):  
Kuo-Wei Huang ◽  
Theo P Goncalves ◽  
Indranil Dutta
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Bifunctional Catalysis ◽  
Conventional Model ◽  
Metal Catalysis ◽  
Metal Ligand

Unlike the conventional model of transition metal catalysis, ligands in metal–ligand cooperative (or bifunctional) catalysis are involved in the substrate activations. Such processes have offered unique mechanistic understandings and led...

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