Cationic Tetra- and Pentacoordinate Complexes of Nickel Based on POCN- and POCOP -Type Pincer Ligands: Synthesis, Characterization, and Ligand Exchange Studies

2021 ◽  
Author(s):  
Naser Rahimi ◽  
Davit Zargarian
Keyword(s):  
Ligand Exchange ◽  
Pincer Complexes ◽  
Pincer Ligands ◽  
Acetonitrile Solutions

Stirring acetonitrile solutions of the charge-neutral pincer complexes (POCN)NiBr (1, POCN= ΚP,ΚC,ΚN-{2-(i-Pr)2PO,6-CH2{c-N(CH2)5}-C6H3) and (POCOP)NiBr (2, POCOP= ΚP,ΚC,ΚP'-2,6-(i-Pr2PO)2}C6H3) with AgSbF6 facilitates Br- abstraction to give the corresponding cationic acetonitrile adducts [(POCN)Ni(NCMe)]+,...

Squeezing Bi: PNP and P2N3 pincer complexes of bismuth

2020 ◽  
Vol 49 (45) ◽  
pp. 16072-16076 ◽  
Author(s):  
Marcus B. Kindervater ◽  
Toren Hynes ◽  
Katherine M. Marczenko ◽  
Saurabh S. Chitnis
Keyword(s):  
Pincer Complexes ◽  
Pincer Ligands

Stable neutral and highly-reactive cationic Bi complexes featuring NNN and PNP pincer ligands are debuted.

Transfer-dehydrogenation of secondary alcohols catalyzed by manganese NNN-pincer complexes

2019 ◽  
Vol 55 (94) ◽  
pp. 14143-14146 ◽  
Author(s):  
Svenja Budweg ◽  
Kathrin Junge ◽  
Matthias Beller
Keyword(s):  
Pincer Complexes ◽  
Pincer Ligands ◽  
Secondary Alcohols ◽  
Catalytic Systems

Novel catalytic systems based on pentacarbonylmanganese bromide and stable NNN-pincer ligands are presented for the transfer-dehydrogenation of secondary alcohols to give the corresponding ketones in good to excellent isolated yields.

scholarly journals Electrodeposition of Fe-Complexes on Oxide Surfaces for Efficient OER Catalysis

Catalysts ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 577
Author(s):  
Sahir M. Al-Zuraiji ◽  
Tímea Benkó ◽  
Krisztina Frey ◽  
Zsolt Kerner ◽  
József S. Pap
Keyword(s):  
Tin Oxide ◽  
Indium Tin Oxide ◽  
Ligand Exchange ◽  
Electrode Materials ◽  
Catalyst Layer ◽  
Pincer Ligands ◽  
Fe Complexes ◽  
Photo Electrode ◽  
Molecular Catalysts ◽  
Oxygen Evolving

Progress in non-covalent/self-assembled immobilization methods on (photo)electrode materials for molecular catalysts could broaden the scope of attainable systems. While covalent linkage (though considered more stable) necessitates functional groups introduced by means of often cumbersome synthetic procedures, non-covalent assemblies require sufficient propensity of the molecular unit for surface adsorption, thus set less rigorous pre-requisites. Herein, we report efficient electrodeposition (ED) of two Fe(III) complexes prepared with closely related NN’N pincer ligands yielding stable and active ad-layers for the electrocatalysis of the oxygen-evolving reaction (OER). The ED method is based on the utilization of a chloride precursor complex [FeIIICl2(NN’N)], which is dissolved in an organic electrolyte undergoes chloride/aqua ligand exchange upon addition of water. ED provides patchy distribution of a chloride-depleted catalyst layer on indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) surfaces, which can be applied for long periods as OER electrocatalysts. Compared to drop-casting or layering of [FeIIICl2(NN’N)] with Nafion (a commonly used support for molecular electrocatalysts), the surface modification by ED is a material saving and efficient method to immobilize catalysts.

scholarly journals Group 11 Pincer Oxazoline Complexes

2021 ◽  
Author(s):  
Mahroo T. Seighalani
Keyword(s):  
Point Group ◽  
Diffraction Method ◽  
Binding Mode ◽  
Group Symmetry ◽  
Pincer Complexes ◽  
Pincer Ligands ◽  
Henry Reaction ◽  
X Ray Diffraction ◽  
Pincer Ligand ◽  
Nitroaldol Reaction

The synthesis and characterization of new copper pincer complexes via cyclometallation of potentially anionic pincer ligands with C1 point group symmetry is reported. All of these complexes have been characterized by single crystal X-ray diffraction method, which confirms the proposed tridentate binding mode of pincer ligand and the formation of an amido N-Cu bond. The reactivity of two of the complexes was investigated towards C-C bond formation reaction, notably the Henry reaction. One of the complexes, which was derived from the achiral pincer ligand, is shown to be a suitable catalyst for the Henry reaction under the standard conditions. The Henry or nitroaldol reaction is one of the organic reactions which affords a C-C bond. The product of this reaction is a β-nitro alcohol which is formed by addition of a nitroalkane to a carbonyl compound.

scholarly journals Asymmetric Bis-PNP Pincer Complexes of Zirconium and Hafnium - a Measure of Hemilability

2020 ◽  
Author(s):  
Celia Idelson ◽  
Leah Webster ◽  
Tobias Krämer ◽  
Mark Chadwick
Keyword(s):  
Nmr Spectroscopy ◽  
Dft Calculations ◽  
Energy Barrier ◽  
Pincer Complexes ◽  
Pincer Ligands ◽  
Direct Contrast ◽  
Vt Nmr

Asymmetrically-bound pyrrollide-based bis-PNP pincer complexes of zirconium and hafnium<br>have been formed. The [κ2-PNPPh][κ3-PNPPh]MCl2 species are in direct contrast to previous<br>zirconium PNP pincer complexes. The pincer ligands are fluxional in their binding and the<br>energy barrier for exchange has been approximated using VT-NMR spectroscopy and the<br>result validated by DFT calculations.

scholarly journals Structural diversity of halocarbonyl molybdenum and tungsten PNP pincer complexes through ligand modifications

2016 ◽  
Vol 45 (35) ◽  
pp. 13834-13845 ◽  
Author(s):  
Sara R. M. M. de Aguiar ◽  
Berthold Stöger ◽  
Ernst Pittenauer ◽  
Günter Allmaier ◽  
Luis F. Veiros ◽  
...  
Keyword(s):  
Comparative Study ◽  
Structural Diversity ◽  
Pincer Complexes ◽  
Pincer Ligands ◽  
And Tungsten

A comparative study of a series of halocarbonyl Mo(ii) and W(ii) complexes featuring PNP pincer ligands based on a 2,6-diaminopyridine scaffold is presented.

Synthesis and Structure of a Novel Substituted Benzothiazolyl-N-phenyl-2-pyridinecarbothioamide; Kinetics of Formation and Electrochemistry of Two of its Palladium Pincer Complexes

2015 ◽  
Vol 68 (5) ◽  
pp. 731 ◽  
Author(s):  
Mark A.W. Lawrence ◽  
Yvette A. Jackson ◽  
Willem H. Mulder ◽  
Per Martin Björemark ◽  
Mikael Håkansson
Keyword(s):  
Complex Formation ◽  
Stability Constant ◽  
Palladium Complex ◽  
Coordination Complexes ◽  
Pincer Complexes ◽  
Kinetics Of Formation ◽  
Acetonitrile Solutions ◽  
The Stability ◽  
Electron Transfers ◽  
Kinetics Of

The synthesis and crystal structures of bis-N-(2,5-dimethoxyphenyl)pyridine-2,6-dicarbothioamide (dicarbothioamide I) and 6-(4,7-dimethoxy-2-benzothiazolyl)-N-(2,5-dimethoxyphenyl)-2-pyridinecarbothioamide (L1) as well as the syntheses of the palladium(ii) chloride and acetate pincer complexes are reported. The stability constant for the palladium complex formation at 25°C was found to be (2.04 ± 0.26) × 104 dm3 mol–1 and (2.30 ± 0.19) × 104 dm3 mol–1 with ΔfH = 8 ± 1 kJ mol–1, ΔfSθ = 108 ± 10 J K–1 mol–1, and ΔfH = 17 ± 4 kJ mol–1 and ΔfSθ = 140 ± 20 J K–1 mol–1 for the PdClL1 and Pd(OAc)L1, respectively. The kinetics of formation of the palladium(ii) complexes were investigated and the mechanism is proposed to be associative in nature (ΔH1‡ = 34 ± 2 kJ mol–1 and ΔS1‡ = –113 ± 8 J K–1 mol–1, and ΔH1‡ = 37 ± 3 kJ mol–1 and ΔS1‡ = –100 ± 8 J K–1 mol–1 for the PdClL1 and Pd(OAc)L1 species, respectively). The electrochemical measurements of the acetonitrile solutions revealed irreversible electron transfers consistent with the electrochemical decomposition of the ligand and its coordination complexes.

scholarly journals Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes

RSC Advances ◽  
2019 ◽  
Vol 9 (37) ◽  
pp. 21116-21124
Author(s):  
Seher Kuyuldar ◽  
Clemens Burda ◽  
William B. Connick
Keyword(s):  
Electron Transfer ◽  
Oxidation Process ◽  
Pincer Complexes ◽  
Pincer Ligands ◽  
Square Planar

Square planar Pt(ii) terpyridine complexes with pincer ligands undergo two-electron oxidation and variation in the ligand substituents allows for tuning of the two-electron oxidation process over a 260 mV range.

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