scholarly journals Advances in f-element cyanide chemistry

2015 ◽  
Vol 44 (17) ◽  
pp. 7727-7742 ◽  
Author(s):  
Jean-Claude Berthet ◽  
Pierre Thuéry ◽  
Michel Ephritikhine
Keyword(s):  
Coordination Modes ◽  
Uranium Complexes ◽  
Cyanide Ligand ◽  
High Valent

By using the cyanide ligand, actinide compounds with unprecedented structures, UIII–CN vs. CeIII–NC and UIII–CN vs. UIV–NC coordination modes, and novel high-valent uranium complexes were revealed.

Carbon Dioxide Activation with Sterically Pressured Mid- and High-Valent Uranium Complexes

2008 ◽  
Vol 130 (37) ◽  
pp. 12536-12546 ◽  
Author(s):  
Suzanne C. Bart ◽  
Christian Anthon ◽  
Frank W. Heinemann ◽  
Eckhard Bill ◽  
Norman M. Edelstein ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Uranium Complexes ◽  
Carbon Dioxide Activation ◽  
High Valent

Kinetic Control of Interpenetration in Fe-Biphenyl-4,4′-dicarboxylate MOFs by Coordination and Oxidation Modulation

2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  
Keyword(s):  
Self Assembly ◽  
Surface Areas ◽  
Metal Precursors ◽  
Additional Coordination ◽  
Fine Control ◽  
Multiple Alternative ◽  
Metal Organic ◽  
Dft Simulations ◽  
High Valent ◽  
And Control

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>

The structure of [Cu(bipy)3][Cu(bipy)(ala)(ClO4)2]ClO4 � a Compound with Two Different Coordination Modes in the same Complex

2008 ◽  
Vol 59 (11) ◽  
Author(s):  
Mircea Braban ◽  
Ionel Haiduc
Keyword(s):  
Solid State ◽  
Chelate Ring ◽  
Octahedral Complex ◽  
State Structure ◽  
Complex Species ◽  
Solid State Structure ◽  
Coordination Modes ◽  
Coordination Center ◽  
Self Assembled ◽  
Chelate Rings

The paper describes the solid state structure of a compound of composition [Cu(bipy)3][Cu(bipy)(ala) (ClO4)2]ClO4, in which both the cation and anion are octahedral complex species with copper(II) as coordination center. The cation contains three chelate rings formed by bipy; the anion contains in the quatorial plane a CuONC2 chelate ring formed by the alaninato ligand and a CuN2C2 chelate ring formed by bipy, with two monodentate perchorato ligands in axial positions completing the six-coordination. In the crystal p-p stackings lead to a supramolecular self-assembled structure.

The versatile coordination chemistry of 1,3-benzenedicarboxylate in the last 20 years: An investigation from the coordination modes to spectroscopic insights

Polyhedron ◽  
2021 ◽  
Vol 198 ◽  
pp. 115068
Author(s):  
Isabelle K.V. Gonçalves ◽  
Willian X.C. Oliveira ◽  
Filipe B. de Almeida ◽  
Maria Vanda Marinho ◽  
Walace D. do Pim ◽  
...  
Keyword(s):  
Coordination Chemistry ◽  
Coordination Modes

High-valent Zirconium-doping modified Co3O4 weave-like nanoarray boosts oxygen evolution reaction

2021 ◽  
pp. 161172
Author(s):  
Guijin Yang ◽  
Botao Zhu ◽  
Yujun Fu ◽  
Jing Zhao ◽  
Yanna Lin ◽  
...  
Keyword(s):  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Zirconium Doping ◽  
High Valent

Endo- and exohedral chloro-fulleride as η5 ligands: A DFT study on the first-row transition metal complexes

2021 ◽  
Author(s):  
Sebastian Anila ◽  
Cherumuttathu Hariharan Suresh
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Dft Study ◽  
C60 Fullerene ◽  
Ring Fusion ◽  
Coordination Modes

C60 fullerene coordinates to transition metals in η2-fashion through its C-C bond at [6,6] ring fusion whereas other coordination modes η3, η4, η5 and η6 are rarely observed. The coordination...

Redefining the Mechanistic Scenario of Carbon–Sulfur Nucleophilic Coupling via High‐Valent Cp*Co(IV) Species

2021 ◽  
Author(s):  
Sara López-Resano ◽  
Sara Martínez de Salinas ◽  
Felipe A. Garcés-Pineda ◽  
Andrea Moneo-Corcuera ◽  
José Ramón Galán-Mascarós ◽  
...  
Keyword(s):  
High Valent
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