Electronic aspects of fungicidal activity in transition metal dithiocarbamate complexes

1975 ◽  
Vol 28 (11) ◽  
pp. 2393 ◽  
Author(s):  
RM Golding ◽  
K Lehtonen ◽  
BJ Ralph
Keyword(s):  
Electronic Structure ◽  
Biological Activity ◽  
Transition Metal ◽  
Spin State ◽  
Metal Ion ◽  
Redox Reactions ◽  
Fungicidal Activity ◽  
Receptor Site ◽  
Iron Ion ◽  
Reversible Redox

In this study of the fungicidal activity of a series of transition metal ion dithiocarbamates in relation to their electronic structure, a model is presented to interpret the biological activity of these complexes, namely the ability of the complex to fit into a receptor site and its ability to undergo reversible redox reactions at suitable potentials. It is shown that in the case of the iron(III) dithiocarbamate complexes these properties are manifested in the spin state of the iron ion.

scholarly journals Density-Based Descriptors of Redox Reactions Involving Transition Metal Compounds as a Reality-Anchored Framework: A Perspective

Molecules ◽  
2021 ◽  
Vol 26 (18) ◽  
pp. 5541
Author(s):  
Daniel Koch ◽  
Mohamed Chaker ◽  
Manabu Ihara ◽  
Sergei Manzhos
Keyword(s):  
Transition Metal ◽  
Metal Ion ◽  
Redox Reactions ◽  
Rational Design ◽  
Chemical Properties ◽  
Transition Metal Ions ◽  
Blind Spot ◽  
Transition Metal Compounds ◽  
Metal Compounds ◽  
Active Transition

Description of redox reactions is critically important for understanding and rational design of materials for electrochemical technologies, including metal-ion batteries, catalytic surfaces, or redox-flow cells. Most of these technologies utilize redox-active transition metal compounds due to their rich chemistry and their beneficial physical and chemical properties for these types of applications. A century since its introduction, the concept of formal oxidation states (FOS) is still widely used for rationalization of the mechanisms of redox reactions, but there exists a well-documented discrepancy between FOS and the electron density-derived charge states of transition metal ions in their bulk and molecular compounds. We summarize our findings and those of others which suggest that density-driven descriptors are, in certain cases, better suited to characterize the mechanism of redox reactions, especially when anion redox is involved, which is the blind spot of the FOS ansatz.

scholarly journals Electron Inventory of the Iron-Sulfur Scaffold Complex HypCD Essential in [NiFe]-Hydrogenase Cofactor Assembly

2021 ◽  
Author(s):  
Sven T. Stripp ◽  
Jonathan Oltmanns ◽  
Christina S. Müller ◽  
David Ehrenberg ◽  
Ramona Schlesinger ◽  
...  
Keyword(s):  
Redox Reactions ◽  
Redox Activity ◽  
Construction Site ◽  
Iron Ion ◽  
Paramagnetic Resonance ◽  
Iron Sulfur ◽  
Reducing Conditions ◽  
Reversible Redox ◽  
Electron Paramagnetic ◽  
Redox Conversion

The [4Fe-4S] cluster containing scaffold complex HypCD is the central construction site for the assembly of the [Fe](CN)2CO cofactor precursor of [NiFe]-hydrogenase. While the importance of the HypCD complex is well established, not much is known about the mechanism by which the CN– and CO ligands are transferred and attached to the iron ion. We developed an efficient protocol for the production and isolation of the functional HypCD complex that facilitated detailed spectroscopic investigations. The results obtained by UV/Vis-, electron paramagnetic Resonance (EPR)-, Resonance Raman-, Fourier-transform infrared (FTIR), and Mössbauer spectroscopy provide comprehensive evidence for an electron inventory fit to drive multi-electron redox reactions. We demonstrate the redox activity of the HypCD complex reporting the interconversion of the [4Fe-4S]2+/+ couple. Additionally, we observed a reversible redox conversion between the [4Fe-4S]2+ and a [3Fe-4S]+ cluster. MicroScale thermophoresis indicated preferable binding between the HypCD complex and its interaction partner HypEF under reducing conditions. Together, these results suggest a redox cascade involving the [4Fe-4S] cluster and a conserved disulfide bond of HypD that may facilitate the synthesis of the [Fe](CN)2CO cofactor precursor on the HypCD scaffold complex.

scholarly journals Pseudocapacitive behavior of the Fe2O3 anode and its contribution to high reversible capacity in lithium ion batteries

Nanoscale ◽  
2018 ◽  
Vol 10 (37) ◽  
pp. 18010-18018 ◽  
Author(s):  
Yimo Xiang ◽  
Zhigao Yang ◽  
Shengping Wang ◽  
Md. Shahriar A. Hossain ◽  
Jingxian Yu ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Oxide ◽  
Lithium Ion Batteries ◽  
Redox Reactions ◽  
Lithium Ion ◽  
Transition Metal Oxide ◽  
Reversible Capacity ◽  
High Reversible Capacity ◽  
Reversible Redox ◽  
Pseudocapacitive Behavior

Pseudocapacitance, which is the storage of charge based on continuous and fast reversible redox reactions at the surface of the electrodes, is commonly observed in transition metal oxide based LIB anodes.

scholarly journals First evidence of light-induced spin transition in molybdenum(iv)

2015 ◽  
Vol 51 (39) ◽  
pp. 8229-8232 ◽  
Author(s):  
N. Bridonneau ◽  
J. Long ◽  
J.-L. Cantin ◽  
J. von Bardeleben ◽  
S. Pillet ◽  
...  
Keyword(s):  
Transition Metal ◽  
Spin State ◽  
Metal Ion ◽  
Zinc Complex ◽  
Spin Transition ◽  
Transition Metal Ion ◽  
Trapping Effect

Photo-induced spin transition in a molybdenum–zinc complex has been evidenced: a unique Light-Induced Excited Spin State Trapping Effect (LIESST) on a 4d transition metal ion.

Kinetic and Mechanistic Aspects of Redox Reactions of Tellurium(Iv) and Tellurium(Vi)

2002 ◽  
Vol 27 (3) ◽  
pp. 127-163 ◽  
Author(s):  
K.G. Sudarsan ◽  
S.N. Dindi
Keyword(s):  
Transition Metal ◽  
Metal Ion ◽  
Redox Reactions ◽  
Mechanistic Studies ◽  
Transition Metal Ion ◽  
Reduction Reactions ◽  
Chromium Vi ◽  
Catalysed Oxidation

Many kinetic and mechanistic studies are reported on the direct and transition metal ion catalysed oxidation of tellurium(IV) with oxidants like persulphate, periodate, chromium(VI), hexacyanoferrate(III), cerium(IV), manganese(III), cobalt(III) etc. Similar studies on the reduction of tellurium(VI) by different reductants are much fewer. An attempt has been made to discuss in brief up-to-date information available on the nature of tellurium(IV) and tellurium(VI) species as well as kinetic and mechanistic studies on the direct and catalysed oxidation and reduction reactions of tellurium(IV) and tellurium(VI) respectively. The majority of reactions concerned with the oxidation of tellurium(IV) to tellurium(VI) seems to prefer a complementary path to a non-complementary one, in accordance with Schaffer's principle of equivalent change.

scholarly journals Electron Inventory of the Iron-Sulfur Scaffold Complex HypCD Essential in [NiFe]-Hydrogenase Cofactor Assembly

2021 ◽  
Author(s):  
Sven T. Stripp ◽  
Jonathan Oltmanns ◽  
Christina S. Müller ◽  
David Ehrenberg ◽  
Ramona Schlesinger ◽  
...  
Keyword(s):  
Redox Reactions ◽  
Redox Activity ◽  
Construction Site ◽  
Iron Ion ◽  
Paramagnetic Resonance ◽  
Iron Sulfur ◽  
Reducing Conditions ◽  
Reversible Redox ◽  
Electron Paramagnetic ◽  
Redox Conversion

The [4Fe-4S] cluster containing scaffold complex HypCD is the central construction site for the assembly of the [Fe](CN)2CO cofactor precursor of [NiFe]-hydrogenase. While the importance of the HypCD complex is well established, not much is known about the mechanism by which the CN– and CO ligands are transferred and attached to the iron ion. We developed an efficient protocol for the production and isolation of the functional HypCD complex that facilitated detailed spectroscopic investigations. The results obtained by UV/Vis-, electron paramagnetic Resonance (EPR)-, Resonance Raman-, Fourier-transform infrared (FTIR), and Mössbauer spectroscopy provide comprehensive evidence for an electron inventory fit to drive multi-electron redox reactions. We demonstrate the redox activity of the HypCD complex reporting the interconversion of the [4Fe-4S]2+/+ couple. Additionally, we observed a reversible redox conversion between the [4Fe-4S]2+ and a [3Fe-4S]+ cluster. MicroScale thermophoresis indicated preferable binding between the HypCD complex and its interaction partner HypEF under reducing conditions. Together, these results suggest a redox cascade involving the [4Fe-4S] cluster and a conserved disulfide bond of HypD that may facilitate the synthesis of the [Fe](CN)2CO cofactor precursor on the HypCD scaffold complex.

scholarly journals Density-based Descriptors of Redox Reactions Involving Transition Metal Compounds as a Reality-anchored Framework: A Perspective

2021 ◽  
Author(s):  
Daniel Koch ◽  
Mohamed Chaker ◽  
Manabu Ihara ◽  
Sergei Manzhos
Keyword(s):  
Transition Metal ◽  
Metal Ion ◽  
Redox Reactions ◽  
Rational Design ◽  
Chemical Properties ◽  
Transition Metal Ions ◽  
Blind Spot ◽  
Transition Metal Compounds ◽  
Metal Compounds ◽  
Active Transition

Description of redox reactions is critically important for understanding and rational design of materials for electrochemical technologies including metal-ion batteries, catalytic surfaces, or redox-flow cells. Most of these technologies utilize redox-active transition metal compounds due to their rich chemistry and their beneficial physical and chemical properties for these types of applications. A century since its introduction, the concept of formal oxidation states (FOS) is still widely used for rationalization of the mechanisms of redox reactions, but there exists a well-documented discrepancy between FOS and the electron density-derived charge states of transition metal ions in their bulk and molecular compounds. We summarize our findings and those of others which suggest that density-driven descriptors are in certain cases better suited to characterize the mechanism of redox reactions, especially when anion redox is involved, which is the blind spot of the FOS ansatz.

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