Synthesis, characterization and semi-empirical calculations for the thiocyanate linkage isomers of an (α-iminooxime)cobalt(III) macrocyclic complex

Cavichiolo, Leandro J.; Hasegawa, T.; Nunes, Fábio Souza

doi:10.1016/j.saa.2005.07.011

Cited by 6 publications

(1 citation statement)

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“…The reduction peaks of Co III (pn)2Cl(L) 2+ are indicating the electron accepting/donating abilities of R of L ligand, that is, m-OCH3 to H in aqueous solution. The electrochemical behaviour of Co(III) complexes is due to the Co III /Co II couples and the negative potential indicates that metal centered reduction [18]. The peak towards negative direction corresponds to Co III /Co II processes, which are irreversible processes.…”

Section: Resultsmentioning

confidence: 99%

Thermal Reduction of CoIII(pn)2Cl(L)2+-Fe(II) Ions in Aqueous-Organic Solvent Medium via Outer-Sphere Electron Transfer Approach

Stephen¹,

Gunasekaran²,

Nalini³

et al. 2018

Asian J. Chem.

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Medium imparts changes in redox reactions of metal complexes. That is, solvent plays an important role in trapping the exchanging electron on one site similar to that of intramolecular structural changes. Especially in ionic reactions, ion can be thought of creating a polarization field in the surrounding solvent. The rationality behind the proposal of the kinetics was detailed by fit the data in correlation equation involving linear and multiple Grunwald-Winstein plot, Swain's dual linear relationship and Kamlet-Taft's equations. The kinetic inferences of outer-sphere electron transfer reactions of cobalt(III) aryl amine complexes (Co III (pn)2Cl(L) 2+ where L = RC6H5NH2, R = m-OCH3, p-F and H) with MeOH/dioxane solvent content were explored at different temperatures.

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Section: Resultsmentioning

confidence: 99%

Thermal Reduction of CoIII(pn)2Cl(L)2+-Fe(II) Ions in Aqueous-Organic Solvent Medium via Outer-Sphere Electron Transfer Approach

Stephen¹,

Gunasekaran²,

Nalini³

et al. 2018

Asian J. Chem.

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Solvent control on the electron transfer reaction between Co^III(en)₂Br(L)²⁺–Fe(CN) (L = aryl amines) by regression relationships: the PXRD and electrochemical investigations

Anbalagan

Lydia

2010

J of Physical Organic Chem

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Solvent shell coupled electron transfer (ET) reaction, principally between CoIII(en)2Br(L)2+ and Fe(CN) 64− complexes (L = RC6H4NH2; R = m‐OCH3, p‐F, H, m‐CH3, p‐CH3, p‐OC2H5, and p‐OCH3) in H2O/EtOH binary mixed solvents has been investigated. The cobalt(III)‐aryl amine complexes have been structurally refined by powder X‐ray diffraction (PXRD) data as monoclinic unit cell with a distorted geometry. Cyclic voltammograms of the complexes exhibit CoIII/CoII and CoII/CoI reduction peaks with an indication of participation of electron accepting/donating abilities of RC6H4NH2 in the reduction. The ΔEp (50–580 mV) and Ic/ν½ (0.12–2.83) values differ for the complexes. ET between CoIII(en)2Br(L)2+ and Fe(CN) 64− is due to ion pair, {CoIII(en)2Br(L)2+; Fe(CN) 64−}, formation leading to product via (i) solvent caged ({CoIII…FeII}, restricted mobility due to RC6H4NH2) and (ii) solvent controlled (electron accepting/donating substituent in aryl ligand concertedly alters the equilibrium: reactants ↔ ion pair) mechanisms. Reduction was followed in 0–30% v/v (x2: xEtOH = 0, 0.0159–0.1162) aqueous ethanol solutions at 286, 293, and 300 K. Reaction follows second‐order condition and there is a gradation in rate when x2 = 0–0.1162 representing co‐solvent influence. This tendency is understood in the attainment of equilibrium and the formed compact ion pair. In order to estimate the solvent influence, the rate data were subjected to linear and multiple regression analyses using Ys = Y0 + a1X1 + a2X2 + a3X3…anXn correlation relationship. Copyright © 2010 John Wiley & Sons, Ltd.

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Molecular structure and linkage isomerization in copper(II) complexes containing N,N-dialkyl-N′-benzylethylenediamine and thiocyanate ligands: a combined crystallographic, spectroscopic and DFT study

Golchoubian

Koohzad

2014

Transition Met Chem

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Synthesis, characterization and semi-empirical calculations for the thiocyanate linkage isomers of an (α-iminooxime)cobalt(III) macrocyclic complex

Cited by 6 publications

References 30 publications

Thermal Reduction of CoIII(pn)2Cl(L)2+-Fe(II) Ions in Aqueous-Organic Solvent Medium via Outer-Sphere Electron Transfer Approach

Thermal Reduction of CoIII(pn)2Cl(L)2+-Fe(II) Ions in Aqueous-Organic Solvent Medium via Outer-Sphere Electron Transfer Approach

Solvent control on the electron transfer reaction between Co^III(en)₂Br(L)²⁺–Fe(CN) (L = aryl amines) by regression relationships: the PXRD and electrochemical investigations

Molecular structure and linkage isomerization in copper(II) complexes containing N,N-dialkyl-N′-benzylethylenediamine and thiocyanate ligands: a combined crystallographic, spectroscopic and DFT study

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Synthesis, characterization and semi-empirical calculations for the thiocyanate linkage isomers of an (α-iminooxime)cobalt(III) macrocyclic complex

Cited by 6 publications

References 30 publications

Thermal Reduction of CoIII(pn)2Cl(L)2+-Fe(II) Ions in Aqueous-Organic Solvent Medium via Outer-Sphere Electron Transfer Approach

Thermal Reduction of CoIII(pn)2Cl(L)2+-Fe(II) Ions in Aqueous-Organic Solvent Medium via Outer-Sphere Electron Transfer Approach

Solvent control on the electron transfer reaction between CoIII(en)2Br(L)2+–Fe(CN) (L = aryl amines) by regression relationships: the PXRD and electrochemical investigations

Molecular structure and linkage isomerization in copper(II) complexes containing N,N-dialkyl-N′-benzylethylenediamine and thiocyanate ligands: a combined crystallographic, spectroscopic and DFT study

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Solvent control on the electron transfer reaction between Co^III(en)₂Br(L)²⁺–Fe(CN) (L = aryl amines) by regression relationships: the PXRD and electrochemical investigations