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Topic: Comparison of reduction potentials for some Iron Complexes  (Read 2006 times)

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Offline T6022

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Comparison of reduction potentials for some Iron Complexes
« on: March 08, 2015, 11:10:36 AM »
I need some help with this table. The problem is to figure out why reduction potential are in this order.

1) Fe(H2O)63+ + e-  :rarrow: Fe(H2O)62+    E°=0.77 V

2)Fe(CN)63- + e-  :rarrow: Fe(CN)64-       E°=0.36 V

3)Fe(phen)33+ + e-  :rarrow: Fe(phen)32+    E°=1.14 V


My hypothesis:

a) Fe3+ is harder than Fe2+, so it tends to bind hard ligand as H2O and phen.
b) CN- is hard, but it stabilizes low oxidation state (due to back-bonding in π*). Maybe for CN- the reduction potential is the lowest because the complex have high negative charge. So equilibrium favours reagent.
c) phen can't accept back-bonding because π-system is delocalized on carbons atoms. In theory this complex shoud have low potential because phen stabilizes high-oxidation state. But it isn't true.

This argument seems inapplicable to this problem. Can anyone help me out?
 
« Last Edit: March 08, 2015, 11:37:18 AM by T6022 »

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