Non-Nernstian Two-Electron Transfer Reactions for Immobilized Molecules: A Theoretical Study in Cyclic Voltammetry

2013 ◽  
Vol 117 (10) ◽  
pp. 5208-5220 ◽  
Author(s):  
Joaquin Gonzalez ◽  
Manuela Lopez-Tenes ◽  
Angela Molina
Keyword(s):  
Electron Transfer ◽  
Cyclic Voltammetry ◽  
Theoretical Study ◽  
Transfer Reactions ◽  
Electron Transfer Reactions

scholarly journals Zur Elektrochemie von Metall(O)-Verbindungen, V [1] Reaktionen von Diazadien-Metall(VIb)-carbonylkationen und -anionen / Electrochemistry of Metal(O) Compounds, V [1] Reactions of Diazadiene Metal(VIb) Carbonyl Cations and Anions

1982 ◽  
Vol 37 (3) ◽  
pp. 324-331 ◽  
Author(s):  
Heindirk torn Dieck ◽  
Ewald Kühl
Keyword(s):  
Electron Transfer ◽  
Cyclic Voltammetry ◽  
Chemical Reactions ◽  
Oxidation States ◽  
Transfer Reactions ◽  
Carbonyl Complexes ◽  
Electron Transfer Reactions ◽  
Reactions With Nucleophiles ◽  
The Stability ◽  
Subsequent Chemical

Abstract Carbonyl complexes of chromium, molybdenum and tungsten of the type DAD M(CO)4 with DAD - diazadiene (R-N=CR′-CR′=NR) are shown by cyclic voltammetry to undergo electron transfer reactions to [DAD M(CO)4]+ and [DAD M(CO)4]-. The rate of subsequent chemical reactions with nucleophiles or by loss of ligands depend on the sol-vent, the metal and the ligands' electronic and steric properties. Chromium(+I) is more readily stabilized than Mo(+I) or W(-I) while the opposite is true for the stability of the anions formed. The dimerisation of a low-coordinate species DAD Mo(CO)3 from the reduction of DAD Mo(CO)3(CH3CN) is detected electrochemically. The stabilization of oxidation states +1 and -I is briefly discussed in view of the DAD ligand properties.

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