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Electroinduced SRN 1 preparative reactions part 1: Estimation of the limiting diffusion currents on various cathodic materials in liquid ammonia and dimethylformamide

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Abstract

Limiting diffusion currents are estimated by an indirect method which consists in determining the chemical yield of substitution product in the electrosynthesis of a biaryl by an SRN type reaction. The limiting diffusion currents can then be deduced from the yields. Different industrial cathodic materials have been investigated both in liquid ammonia (−40° C) and dimethylformamide (20°C). The limiting diffusion currents are generally about 2.8 times larger in ammonia than in dimethyl-formamide.

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Abbreviations

R :

yield in biaryl with respect to the reacted aromatic halide

k d :

diffusion rate constant

k 2 :

rate constant of the key-reaction between Ar• and Nu−

A :

cathode area

D :

diffusion coefficient of the mediator

D 1 :

diffusion coefficient of mediator P 1

D 2 :

diffusion coefficient of mediator P 2 (in the same medium as for D 1)

D NH 3 :

diffusion coefficient of the mediator in NH3

D DMF :

diffusion coefficient of the mediator in DMF

D 2,NH 3 :

diffusion coefficient of mediator P1 in NH3

D 2,NH 3 :

diffusion coefficient of mediator P2 in NH3

D 2,DMF :

diffusion coefficient of mediator P2 in DMF

δ:

diffusion layer thickness

δNH 3 :

diffusion layer thickness in NH3

δDMF :

diffusion layer thickness in DMF

i lim :

limiting diffusion current of the mediator

I lim :

limiting diffusion current of the mediator per unit of concentration of the mediator

I lim :

limiting diffusion current of the mediator per unit of concentration of the mediator and per unit of cathode area

I lim,NH 3 :

limiting diffusion current of the mediator in NH3 (normalized with respect to the cathode area and the concentration)

I lim,DMF :

limiting diffusion current of the mediator in DMF (normalized with respect to the cathode area and the concentration)

ip :

reduction peak current of the mediator

ip NH 3 :

reduction peak current of the mediator in NH3 (measured by cyclic voltammetry)

ip DMF :

reduction peak current of the mediator in DMF (measured by cyclic voltammetry in the same conditions of concentration, cathode and scan speed as in NH3)

Ψ:

solvent association factor

M s :

solvent molecular weight

η:

solvent absolute viscosity

V :

substrate molecular volume

V 1 :

molecular volume of mediator P1

V 2 :

molecular volume of mediator P2

ω:

rotation speed of the electrode

ν:

kinematic viscosity, ν = η/d

d :

solvent density

ArH :

amount of reduction product, mol

ArNu :

amount of coupling product, mol

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Authors and Affiliations

  1. Laboratoire de Chimie et Electrochimie des Matériaux Moléculaires, ESPC1 10, rue Vauquelin, 75231, Paris Cedex 05, France

    C. Combellas, Y. Lu & A. Thiebault

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  1. C. Combellas
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  2. Y. Lu
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  3. A. Thiebault
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Combellas, C., Lu, Y. & Thiebault, A. Electroinduced SRN 1 preparative reactions part 1: Estimation of the limiting diffusion currents on various cathodic materials in liquid ammonia and dimethylformamide. J Appl Electrochem 23, 841–847 (1993). https://doi.org/10.1007/BF00249958

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  • DOI: https://doi.org/10.1007/BF00249958

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