Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes
Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that...
Ausführliche Beschreibung
Gespeichert in:
| Autor*in: |
Galijasevic, Semira [verfasserIn] |
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| Format: |
Artikel |
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| Sprache: |
Englisch |
| Erschienen: |
2013 |
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| Schlagwörter: |
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| Anmerkung: |
© Springer Science+Business Media Dordrecht 2013 |
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| Übergeordnetes Werk: |
Enthalten in: Transition metal chemistry - Springer Netherlands, 1975, 38(2013), 8 vom: 05. Okt., Seite 883-890 |
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| Übergeordnetes Werk: |
volume:38 ; year:2013 ; number:8 ; day:05 ; month:10 ; pages:883-890 |
| Links: |
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| DOI / URN: |
10.1007/s11243-013-9763-z |
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OLC208404927X |
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| 520 | |a Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. | ||
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10.1007/s11243-013-9763-z doi (DE-627)OLC208404927X (DE-He213)s11243-013-9763-z-p DE-627 ger DE-627 rakwb eng 660 VZ Galijasevic, Semira verfasserin aut Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes 2013 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier © Springer Science+Business Media Dordrecht 2013 Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. Copper Complex Donor Atom Nitrogen Donor Atom Blue Copper Protein Atom Inversion Enthalten in Transition metal chemistry Springer Netherlands, 1975 38(2013), 8 vom: 05. Okt., Seite 883-890 (DE-627)129605417 (DE-600)242084-3 (DE-576)015099652 0340-4285 nnns volume:38 year:2013 number:8 day:05 month:10 pages:883-890 https://doi.org/10.1007/s11243-013-9763-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_70 GBV_ILN_4012 GBV_ILN_4125 AR 38 2013 8 05 10 883-890 |
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10.1007/s11243-013-9763-z doi (DE-627)OLC208404927X (DE-He213)s11243-013-9763-z-p DE-627 ger DE-627 rakwb eng 660 VZ Galijasevic, Semira verfasserin aut Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes 2013 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier © Springer Science+Business Media Dordrecht 2013 Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. Copper Complex Donor Atom Nitrogen Donor Atom Blue Copper Protein Atom Inversion Enthalten in Transition metal chemistry Springer Netherlands, 1975 38(2013), 8 vom: 05. Okt., Seite 883-890 (DE-627)129605417 (DE-600)242084-3 (DE-576)015099652 0340-4285 nnns volume:38 year:2013 number:8 day:05 month:10 pages:883-890 https://doi.org/10.1007/s11243-013-9763-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_70 GBV_ILN_4012 GBV_ILN_4125 AR 38 2013 8 05 10 883-890 |
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10.1007/s11243-013-9763-z doi (DE-627)OLC208404927X (DE-He213)s11243-013-9763-z-p DE-627 ger DE-627 rakwb eng 660 VZ Galijasevic, Semira verfasserin aut Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes 2013 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier © Springer Science+Business Media Dordrecht 2013 Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. Copper Complex Donor Atom Nitrogen Donor Atom Blue Copper Protein Atom Inversion Enthalten in Transition metal chemistry Springer Netherlands, 1975 38(2013), 8 vom: 05. Okt., Seite 883-890 (DE-627)129605417 (DE-600)242084-3 (DE-576)015099652 0340-4285 nnns volume:38 year:2013 number:8 day:05 month:10 pages:883-890 https://doi.org/10.1007/s11243-013-9763-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_70 GBV_ILN_4012 GBV_ILN_4125 AR 38 2013 8 05 10 883-890 |
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10.1007/s11243-013-9763-z doi (DE-627)OLC208404927X (DE-He213)s11243-013-9763-z-p DE-627 ger DE-627 rakwb eng 660 VZ Galijasevic, Semira verfasserin aut Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes 2013 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier © Springer Science+Business Media Dordrecht 2013 Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. Copper Complex Donor Atom Nitrogen Donor Atom Blue Copper Protein Atom Inversion Enthalten in Transition metal chemistry Springer Netherlands, 1975 38(2013), 8 vom: 05. Okt., Seite 883-890 (DE-627)129605417 (DE-600)242084-3 (DE-576)015099652 0340-4285 nnns volume:38 year:2013 number:8 day:05 month:10 pages:883-890 https://doi.org/10.1007/s11243-013-9763-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_70 GBV_ILN_4012 GBV_ILN_4125 AR 38 2013 8 05 10 883-890 |
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10.1007/s11243-013-9763-z doi (DE-627)OLC208404927X (DE-He213)s11243-013-9763-z-p DE-627 ger DE-627 rakwb eng 660 VZ Galijasevic, Semira verfasserin aut Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes 2013 Text txt rdacontent ohne Hilfsmittel zu benutzen n rdamedia Band nc rdacarrier © Springer Science+Business Media Dordrecht 2013 Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. Copper Complex Donor Atom Nitrogen Donor Atom Blue Copper Protein Atom Inversion Enthalten in Transition metal chemistry Springer Netherlands, 1975 38(2013), 8 vom: 05. Okt., Seite 883-890 (DE-627)129605417 (DE-600)242084-3 (DE-576)015099652 0340-4285 nnns volume:38 year:2013 number:8 day:05 month:10 pages:883-890 https://doi.org/10.1007/s11243-013-9763-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_OLC SSG-OLC-TEC SSG-OLC-CHE GBV_ILN_70 GBV_ILN_4012 GBV_ILN_4125 AR 38 2013 8 05 10 883-890 |
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Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes |
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Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes |
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Galijasevic, Semira |
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Transition metal chemistry |
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thermodynamic and electron-transfer properties of copper(ii/i) polyaminothiaether complexes |
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Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes |
| abstract |
Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. © Springer Science+Business Media Dordrecht 2013 |
| abstractGer |
Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. © Springer Science+Business Media Dordrecht 2013 |
| abstract_unstemmed |
Abstract In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented. © Springer Science+Business Media Dordrecht 2013 |
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Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes |
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