Metal ion and ligand dependency of the redox behaviour of some first row transition metal dithiocarbamates

1973 ◽  
Vol 26 (11) ◽  
pp. 2533 ◽  
Author(s):  
R Chant ◽  
AR Hendrickson ◽  
RL Martin ◽  
NM Rohde
Keyword(s):  
Transition Metal ◽  
Redox Potential ◽  
Metal Ion ◽  
Electron Configuration ◽  
Redox Potentials ◽  
Redox Behaviour ◽  
Reduction Processes ◽  
Metal Dithiocarbamates ◽  
The One ◽  
Marked Dependence

The one-electron oxidation and reduction processes for some 80 dithiocarbamates of Cr, Mn, Fe, Co, Ni, and Cu reveal a marked dependence of redox potential on the metal 3dn electron configuration. For all the complexes examined, the relative ordering of the redox potentials with the dithiocarbamate substituents is remarkably consistent for both oxidation and reduction processes.

scholarly journals The redox potentials of the two-iron plant algal ferredoxins. An electrostatic model

1973 ◽  
Vol 133 (2) ◽  
pp. 283-287 ◽  
Author(s):  
R. J. Kassner ◽  
W. Yang
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Redox Potential ◽  
Negative Charge ◽  
Electrostatic Model ◽  
Redox Potentials ◽  
Electron Transfer Proteins ◽  
Electrostatic Free Energy ◽  
The One ◽  
Charged Ions

The two-iron–sulphur co-ordination centre in plant and algal ferredoxins is considered as a collection of charged ions whose net negative charge is twice that of the one-iron–sulphur protein rubredoxin. Calculation of the electrostatic free-energy changes for reduction of the two types of proteins indicates that the redox potential of the two-iron–sulphur proteins should be more negative than that of the one-iron–sulphur protein and that in biological systems the ferredoxins should function as one-electron transfer proteins.

One-electron redox kinetics of aqueous transition metal couples Zn2+/+, Co2+/+, and Ni2+/+ using pulse radiolysis

2020 ◽  
Vol 22 (34) ◽  
pp. 19046-19058 ◽  
Author(s):  
Alexandra Lisovskaya ◽  
Kotchaphan Kanjana ◽  
David M. Bartels
Keyword(s):  
Transition Metal ◽  
Pulse Radiolysis ◽  
Redox Potentials ◽  
Redox Kinetics ◽  
Upper Limits ◽  
The One ◽  
Kinetics Of

The one-electron redox potentials for aqueous metal couples Co2+/+ and Ni2+/+ have been investigated by pulse radiolysis using their reactions with a series of reference compounds to establish the most positive upper limits of E0.

Effect of solvent binding on UV-vis spectra and redox potentials of octaethylporphyrins containing first-row transition metal ions

2009 ◽  
Vol 13 (12) ◽  
pp. 1233-1242 ◽  
Author(s):  
Weihua Zhu ◽  
Xiaofeng Zhao ◽  
Zhongping Ou ◽  
Fan Zhou ◽  
Xiaohong Wang ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Ions ◽  
Metal Ion ◽  
Binding Constants ◽  
Transition Metal Ions ◽  
Donor Number ◽  
Central Metal ◽  
Redox Potentials ◽  
Visible Spectra ◽  
Uv Visible

The UV-visible spectra and oxidation/reduction potentials for six octaethylporphyrins with first-row transition metal ions were measured in four non-aqueous solvents and then analyzed as a function of the Gutmann solvent parameters, donor number (DN) or acceptor number (AN). The utilized solvents were dichloromethane ( CH2Cl2 ), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and pyridine (py). The investigated porphyrins were (OEP)M, where OEP = the dianion of octaethylporphyrin and M = CoII, NiII, CuII, ZnII, FeIIICl or MnIIICl . UV-visible spectra upon solvent (S) binding to give (OEP)M(S) or [ (OEP)M(S)2]+Cl- were monitored during a titration of the porphyrin in CH2Cl2 and formation constants ( logβ n, n = 1 or 2) for the ligand addition reactions were determined using standard equations. Five-coordinate (OEP)CoII(S) and (OEP)ZnII(S) are generated in CH2Cl2 solutions containing DMF, DMSO or py while six-coordinate [ (OEP)Mn(S)2]+Cl and [ (OEP)Fe(S)2]+Cl- are formed under the same solution conditions. The magnitudes of the solvent binding constants are discussed in terms of both the solvent donor/acceptor properties and the electronegativity (EN) or stability index (SI) of the porphyrin central metal ion. A comparison between solvent binding constants measured in this study for (OEP)M and literature data for (TPP)M with the same central metal ions is presented.

Transition-metal ion-mediated morphological transformation of pyridine-based peptide nanostructures

2021 ◽  
Vol 45 (1) ◽  
pp. 153-161
Author(s):  
Narendra Singh ◽  
Ramesh Singh ◽  
Swati Sharma ◽  
Khushboo Kesharwani ◽  
Khashti Ballabh Joshi ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Ion ◽  
Chemical Structure ◽  
Morphological Transformation ◽  
Transition Metal Ion

Pyridine-mediated constitutionally isomeric artificial metallopeptides possess remarkable advantages over the natural counterparts mainly due to their tailor-made chemical structure.

scholarly journals Role of redox-inactive metals in controlling the redox potential of heterometallic manganese–oxido clusters

2021 ◽  
Author(s):  
Keisuke Saito ◽  
Minesato Nakagawa ◽  
Manoj Mandal ◽  
Hiroshi Ishikita
Keyword(s):  
Photosystem Ii ◽  
Redox Potential ◽  
Quantum Chemical Calculations ◽  
Catalytic Reaction ◽  
Quantum Chemical ◽  
Ionic Radius ◽  
Redox Potentials ◽  
Oxygen Evolving ◽  
Highest Occupied Molecular Orbitals

AbstractPhotosystem II (PSII) contains Ca2+, which is essential to the oxygen-evolving activity of the catalytic Mn4CaO5 complex. Replacement of Ca2+ with other redox-inactive metals results in a loss/decrease of oxygen-evolving activity. To investigate the role of Ca2+ in this catalytic reaction, we investigate artificial Mn3[M]O2 clusters redox-inactive metals  [M] ([M]  = Mg2+, Ca2+, Zn2+, Sr2+, and Y3+), which were synthesized by Tsui et al. (Nat Chem 5:293, 2013). The experimentally measured redox potentials (Em) of these clusters are best described by the energy of their highest occupied molecular orbitals. Quantum chemical calculations showed that the valence of metals predominantly affects Em(MnIII/IV), whereas the ionic radius of metals affects Em(MnIII/IV) only slightly.

scholarly journals On the Coordination Role of Pyridyl-Nitrogen in the Structural Chemistry of Pyridyl-Substituted Dithiocarbamate Ligands

Crystals ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 286
Author(s):  
Edward R.T. Tiekink
Keyword(s):  
Transition Metal ◽  
Main Group ◽  
Group Element ◽  
Systematic Research ◽  
Pyridyl Nitrogen ◽  
General Observation ◽  
Supramolecular Architectures ◽  
Main Group Element ◽  
Metal Dithiocarbamates

A search of the Cambridge Structural Database was conducted for pyridyl-substituted dithiocarbamate ligands. This entailed molecules containing both an NCS2− residue and pyridyl group(s), in order to study their complexation behavior in their transition metal and main group element crystals, i.e., d- and p-block elements. In all, 73 different structures were identified with 30 distinct dithiocarbamate ligands. As a general observation, the structures of the transition metal dithiocarbamates resembled those of their non-pyridyl derivatives, there being no role for the pyridyl-nitrogen atom in coordination. While the same is true for many main group element dithiocarbamates, a far greater role for coordination of the pyridyl-nitrogen atoms was evident, in particular, for the heavier elements. The participation of pyridyl-nitrogen in coordination often leads to the formation of dimeric aggregates but also one-dimensional chains and two-dimensional arrays. Capricious behaviour in closely related species that adopted very different architectures is noted. Sometimes different molecules comprising the asymmetric-unit of a crystal behave differently. The foregoing suggests this to be an area in early development and is a fertile avenue for systematic research for probing further crystallization outcomes and for the rational generation of supramolecular architectures.

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