Mechanistic Insights into the Oxidative Coupling of N-Heterocyclic Carbenes within the Coordination Sphere of Copper Complexes

2014 ◽  
Vol 20 (40) ◽  
pp. 12729-12733 ◽  
Author(s):  
Benjamin R. M. Lake ◽  
Alireza Ariafard ◽  
Charlotte E. Willans
Keyword(s):  
Coordination Sphere ◽  
Oxidative Coupling ◽  
Copper Complexes ◽  
Heterocyclic Carbenes

scholarly journals Copper catalysis with redox-active ligands

2020 ◽  
Vol 16 ◽  
pp. 858-870 ◽  
Author(s):  
Agnideep Das ◽  
Yufeng Ren ◽  
Cheriehan Hessin ◽  
Marine Desage-El Murr
Keyword(s):  
Electron Transfer ◽  
Coordination Sphere ◽  
Copper Complexes ◽  
Heterocyclic Carbenes ◽  
Metal Center ◽  
Copper Catalysis ◽  
Redox Active Ligands ◽  
Elementary Steps ◽  
Cooperative Catalysis ◽  
Redox Active

Copper catalysis finds applications in various synthetic fields by utilizing the ability of copper to sustain mono- and bielectronic elementary steps. Further to the development of well-defined copper complexes with classical ligands such as phosphines and N-heterocyclic carbenes, a new and fast-expanding area of research is exploring the possibility of a complementing metal-centered reactivity with electronic participation by the coordination sphere. To achieve this electronic flexibility, redox-active ligands can be used to engage in a fruitful “electronic dialogue” with the metal center, and provide additional venues for electron transfer. This review aims to present the latest results in the area of copper-based cooperative catalysis with redox-active ligands.

scholarly journals Using internal electrostatic fields to manipulate the valence manifolds of copper complexes

2021 ◽  
Author(s):  
Alexander B. Weberg ◽  
Samuel P. McCollom ◽  
Laura M. Thierer ◽  
Michael R. Gau ◽  
Patrick J. Carroll ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Copper Complexes ◽  
Photophysical Properties ◽  
Redox Potentials ◽  
Electrostatic Effects ◽  
Electrostatic Fields ◽  
Secondary Coordination Sphere

Secondary coordination sphere electrostatic effects tune the valence manifolds of copper centers, impacting molecular geometries, photophysical properties, and redox potentials.

Aktivierung von CO2 an Übergangsmetallzentren: Struktur und Reaktivität eines C-C-Kopplungsproduktes von CO2 und 2.3-Dimethylbutadien am elektronenreichen Nickel(O) / Activation of CO2 at Transition Metal Centers: Structure and Reactivity of a C-C-Coupling Product of CO2 and 2,3-Dimethylbutadiene at Electron-Rich Nickel(O)

1983 ◽  
Vol 38 (7) ◽  
pp. 835-840 ◽  
Author(s):  
Dirk Walther ◽  
Eckhard Dinjus ◽  
Joachim Sieler ◽  
Nguyen Ngoc Thanh ◽  
Wolfgang Schade ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Transition Metal ◽  
Carboxylic Acids ◽  
Coordination Sphere ◽  
Oxidative Coupling ◽  
Central Atom ◽  
Carboxylate Group ◽  
Metal Centers ◽  
X Ray ◽  
Unsaturated Carboxylic Acids

Carbon dioxide reacts with 2,3-dimethylbutadiene and bis-cyclooctadiene(1,5)-nickel(O) in the presence of N,N′-tetramethyl-ethylendiamine (tmeda) to form [(3,4,5-η3)-3,4-dimethyl-3-pentenylato](N,N′-tetramethyl-ethylendiamine)-nickel(II) as the product of the oxidative coupling of CO2 and the diene. The deep red complex crystallizes in the rhombic space group Pbca. The structure was determined by an X-ray analysis. The monodendate carboxylate group, the π-allyl system and a N-atom of tmeda form a planar coordination sphere around the central atom. The distance between Ni and the second N-atom of tmeda is very long (2.314 Å). Reaction of the complex with R−X (R: H, CH3) yield 3-unsaturated carboxylic acids; tmeda can be substituted by 2,2′-bipyridine.

Syntheses, crystal structures and photophysical properties of Cu(ii) complexes: fine tuning of a coordination sphere for selective binding of azamethiphos

2017 ◽  
Vol 46 (3) ◽  
pp. 985-994 ◽  
Author(s):  
Pushap Raj ◽  
Amanpreet Singh ◽  
Ajnesh Singh ◽  
Narinder Singh
Keyword(s):  
Crystal Structures ◽  
Coordination Sphere ◽  
Copper Complexes ◽  
Photophysical Properties ◽  
Fine Tuning ◽  
Selective Binding

We have synthesized two copper complexesC1–2and these complexes were explored as chemosensors for selective binding with azamethiphos.

From Prochiral N-Heterocyclic Carbenes (NHC) to Optically Pure Copper Complexes: New Opportunities in Asymmetric Catalysis

2019 ◽  
Author(s):  
Lingyu Kong ◽  
Jennifer Morvan ◽  
Delphine Pichon ◽  
Marion Jean ◽  
Muriel Albalat ◽  
...  
Keyword(s):  
Asymmetric Catalysis ◽  
Copper Complexes ◽  
Pure Copper ◽  
Heterocyclic Carbenes ◽  
Allylic Alkylation ◽  
Chiral Hplc ◽  
Pure Cu ◽  
First Time ◽  
Optically Pure ◽  
Cu Complexes

Well-defined optically pure copper-complexes are obtained from prochiral N- Heterocyclic Carbene (NHC) ligands. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces axial chirality. Configurationally stable (Sa)- and (Ra)-atropisomers of various Cu-complexes are isolated by preparative chiral HPLC in nearly quantitative yields and excellent optical purities (>99.5%). Their catalytic performances are illustrated in asymmetric allylic alkylation with high regioselectivity and enantioinductions. Importantly, the carbene transfer from an optically pure Cu-complex to gold or palladium center reveals, for the first time, a full stereoretentivity, supporting the hypothesis of an associative mechanism for the transmetalation.

Chiral imidazo[1,5-a]tetrahydroquinoline N-heterocyclic carbenes and their copper complexes for asymmetric catalysis

2013 ◽  
Vol 24 (8) ◽  
pp. 492-498 ◽  
Author(s):  
Jin-Long Zhang ◽  
Liang-An Chen ◽  
Rui-Bin Xu ◽  
Chuan-Fei Wang ◽  
Yuan-Ping Ruan ◽  
...  
Keyword(s):  
Asymmetric Catalysis ◽  
Copper Complexes ◽  
Heterocyclic Carbenes

Donor-Set-Induced Coordination Sphere and Oxidation-State Switching in the Copper Complexes of O2S2X (X = S, O and NH) Macrocycles

2009 ◽  
Vol 48 (17) ◽  
pp. 8186-8191 ◽  
Author(s):  
Minhye Jo ◽  
Joobeom Seo ◽  
Moo Lyong Seo ◽  
Kyu Seong Choi ◽  
Seong Keuck Cha ◽  
...  
Keyword(s):  
Oxidation State ◽  
Coordination Sphere ◽  
Copper Complexes ◽  
State Switching
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