Ferrocene methanol determination

A stable configuration can only be achieved when nonaqueous solvents are involved. For example, a photoelectro-chemical cell can be operated using the ferrocene/ferrocinium couple at an n-type Si electrode in a pure methanol solvent. This system is of special interest because the rate-determining steps can be analyzed in detail. Using Si as an electrode in CH3OH or CH3CN requires that the solvent is completely water free in order... 

In case of acetonitrile (CHaCN) or deuterated acetonitrile (CDaCN), a Ag wire, placed in the electrolyte solution with 0.01 M AgNOa (Ag/Ag 0.01 M) was used. The potential was determined to 0.082 V against ferrocene. For methanol (CH3OH) or deuterated methanol (CD3OD) a AgCl coated Ag wire, placed in the electrolyte solution, saturated with LiCl (Ag/AgCl sat. LiCl), was used as reference electrode. The potential against ferrocene was 0.458 V,... 

A mixture of VOj and in HCIO4 gives a labile mixed-valence complex [ 203] with a formation constant of 8.1 M. The IT band is detected at 10,100cm". In methanol solution, a number of sulfur-bound copper(II) complexes, models for blue copper proteins, are reduced by ferrocene in a mechanism which involves formation of a precursor ion pair followed by rate-determining electron transfer. The activation parameters suggest that the precursor complex undergoes desolvation in the transition state. 

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