Reaction entropies of redox reactions of transition-metal complexes with sulfur donor ligands

1984 ◽  
Vol 23 (21) ◽  
pp. 3298-3303 ◽  
Author(s):  
J. E. J. Schmitz ◽  
J. G. M. Van der Linden
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Redox Reactions ◽  
Donor Ligands ◽  
Sulfur Donor Ligands ◽  
Sulfur Donor

Übergangsmetallkomplexe mit Schwefelliganden, LXI / Transition Metal Complexes with Sulfur Ligands, LXI

1991 ◽  
Vol 46 (5) ◽  
pp. 673-681 ◽  
Author(s):  
Dieter Sellmann ◽  
Klaus Höhn ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Unpaired Electron ◽  
Redox Reactions ◽  
Similar Process ◽  
Mild Conditions ◽  
No Release

18 and 19 electron NO complexes with the [Fe'buS5'] moiety ('buS5'2- = dianion of 2,2′-bis-(2-mercapto-3,5-di-tertiary-butylphenylthio)diethylsulfide) have been isolated and converted reversibly into each other. The unpaired electron in meso-[Fe(NO)′buS5'], meso-1, is delocalized over the whole molecule and occupies an orbital that is antibonding with respect to Fe– N and Fe–S bonds. Consequently, the NO ligand is readily substituted under mild conditions. In contrast, the 18 electron complex meso-[Fe(NO)'buS5']PF6, meso-2, is entirely inert towards substitution. To our knowledge the exchange of NO by CO in meso-1 via meso-2 is the first example, in which NO is displaced by CO in an isolable NO complex. The NO release from meso-1 via meso-2 can be considered a model for reversible NO bonding in sulfur coordinated metal centres of nitrogenase. It is shown that one-electron redox reactions make stable Fe–NO bonds labile, and the reversible coordination and decoordination of NO in nitrogenase may be induced by a similar process.

Binuclear transition metal complexes of bicompartmental SNO donor ligands: synthesis, characterization, and electrochemistry

2010 ◽  
Vol 63 (8) ◽  
pp. 1451-1461 ◽  
Author(s):  
Naveen V. Kulkarni ◽  
M.P. Sathisha ◽  
Srinivasa Budagumpi ◽  
Gurunath S. Kurdekar ◽  
Vidyanand K. Revankar
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Donor Ligands
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