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

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.

scholarly journals Control of cerium oxidation state through metal complex secondary structures

2015 ◽  
Vol 6 (12) ◽  
pp. 6925-6934 ◽  
Author(s):  
Jessica R. Levin ◽  
Walter L. Dorfner ◽  
Patrick J. Carroll ◽  
Eric J. Schelter
Keyword(s):  
Alkali Metal ◽  
Metal Complex ◽  
Oxidation State ◽  
Coordination Sphere ◽  
Electronic Structures ◽  
Secondary Structures ◽  
Secondary Coordination Sphere

A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation.

New Bond-Valence Sum Model

1997 ◽  
Vol 53 (6) ◽  
pp. 885-894 ◽  
Author(s):  
J. P. Naskar ◽  
S. Hati ◽  
D. Datta
Keyword(s):  
Oxidation State ◽  
Coordination Sphere ◽  
Metal Ion ◽  
Nickel Complexes ◽  
Bond Valence ◽  
Oxidation States ◽  
Linear Variation ◽  
Axial Bond ◽  
Inorganic Complexes ◽  
Bond Valence Sum

A new expression is devised empirically to accommodate zero and some negative oxidation states in the bond-valence sum approach. The method is worked out in detail for a number of homoleptic copper and nickel complexes of various coordinating atoms in several oxidation states of the metals. An implication of the expression is a linear variation between 1/r eq and 1/r ax in octahedral MX 6 moieties, where r eq and r ax are, respectively, the average equatorial and axial bond lengths. This is verified in Cu2+ X 6 chromophores for X = F, O, N and S. The usefulness of the new expression in assessing the compatibility of a coordination sphere with an oxidation state of a metal ion is demonstrated by exemplary applications to some inorganic complexes, azurin and urease.

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.

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 Crystal structures of two unusual, high oxidation state, 16-electron iridabenzenes

2015 ◽  
Vol 71 (11) ◽  
pp. 1315-1318 ◽  
Author(s):  
Daniel T. Chase ◽  
Lev N. Zakharov ◽  
Michael M. Haley
Keyword(s):  
Crystal Structures ◽  
Oxidation State ◽  
Coordination Sphere ◽  
Basal Plane ◽  
Structural Elucidation ◽  
Coordination Geometry ◽  
High Oxidation State ◽  
Apical Position ◽  
Coordination Site ◽  
High Oxidation

Treatment of carbonyl(1,2-diphenylpenta-1,3-dien-1-yl-5-ylidene)bis(triphenylphosphane)iridium, [IrCO(—C(Ph)=C(Ph)—CH=CH—CH=)(PPh3)2], with either bromine or iodine produced dibromido(1,2-diphenylpenta-1,3-dien-1-yl-5-ylidene)(triphenylphosphine)iridium(III), [IrBr2{—C(Ph)=C(Ph)—CH=CH—CH=}(PPh3)], (I), and (1,2-diphenylpenta-1,3-dien-1-yl-5-ylidene)diiodido(triphenylphosphane)iridium(III), [IrI2{—C(Ph)=C(Ph)—CH=CH—CH=}(PPh3)], (II), respectively, which are two rare examples of 16-electron metallabenzenes. Structural elucidation of (I) and (II) reveals that these isotypic iridabenzenes are unusual, not only in their electron count, but also in their coordination sphere of the IrIIIatom where they contain an apparent open coordination site. The crystal structures of (I) and (II) confirm that the molecules are complexes containing five-coordinated IrIIIwith only one triphenylphosphine group bound to the iridium atom, unambiguously proving that the molecules are indeed 16-electron, high-oxidation-state iridabenzenes. The coordination geometry of the IrIIIatom in both structures can be best described as a distorted square pyramid with the P, two Br (or I) and one C atom in the basal plane and another C atom in the apical position.

scholarly journals A Theoretical Study on the Inclusion of Fe, Cu, and Zn in Illite Clays

2019 ◽  
Vol 2019 ◽  
pp. 1-14
Author(s):  
Antonio Sánchez-Coronilla ◽  
Elisa I. Martín ◽  
Francisco José Fernández-de-Cordova ◽  
Francisco Javier Santos ◽  
José Hidalgo Toledo
Keyword(s):  
Dft Calculations ◽  
Oxidation State ◽  
Coordination Sphere ◽  
Theoretical Study ◽  
Oxidation States ◽  
Adsorption Characteristic ◽  
Periodic Dft Calculations ◽  
Periodic Dft ◽  
Cu And Zn ◽  
Oxygen Interaction

The inclusion of Fe, Cu, and Zn in (1, 0, 0), (0, 0.5, 0), and (0.5, 0.5, 0.5) sites of an illite with the KAl2Si4O12H2 structure has been studied. For the inclusion of the metals, their common oxidation states were chosen, that is, 0, +2, +3 and 0, +1, +2, for Fe and Cu, respectively, while 0 and +2 for Zn. Periodic DFT calculations were performed to know the most favourable site of incorporation of the ions. Energetically the most favourable site for the inclusion corresponds to the (1, 0, 0) coordinate for all the ions independently of their oxidation state. However, the highest oxidation state of the metals (Fe3+, Cu2+, and Zn2+) was the most favoured for being incorporated into the illite structure and was the selected ion for the discussion. In those structures, metal oxygen interaction plays an important role in stabilizing the systems. Structural and energetic results indicate that illite presents good adsorption characteristic of those Fe3+, Cu2+, and Zn2+ in the (1, 0, 0) site. Thus, those ions may be available for plants for its extraction by phytoextraction techniques and the consequent soil regeneration. The inclusion of a second metallic ion revealed the most favourable inclusion corresponding to the inclusion of Fe3+ ion. The inclusion of this ion modifies the coordination sphere around the first metal being available for subsequent extraction by phytoremediation or other techniques for clean-up of the soil and its regeneration.

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