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. Author manuscript; available in PMC: 2013 Nov 14.
Published in final edited form as: J Am Chem Soc. 2012 Nov 5;134(45):18843–18852. doi: 10.1021/ja309216v

Table 4.

Selected Electrocatalytic Properties of Protonated Derivatives of 1 and 2.

Catalyst Acid Linear
Region
[H+](mM)		 Plateau
Region
[H+] (mM)		 (ic/ip)maxa k (s−1) Ecatb
(V vs Fc+/0)		 Overpotentialc
(V)
[HFe2(adtNH)(CO)2(dppv)2]+,
[t-H1NH]+ 		ClCH2CO2H 50–400 600–1200 69 5000 −1.49 0.71
HFe2(adtNHH)(CO)2(dppv)2]2+,
[t-H1NH2]2+ 		CF3CO2H 20–280 370–750 167 58000 −1.11 0.51
[Fe2(adtNH)(µ-H)(CO)2(dppv)2+,
[µ-H1NH]+ 		ClCH2CO2H 2–50 60–90 10 20 −1.72 0.90
[HFe2(pdt)(CO)2(dppv)2]+,
[t-H2]+ 		HBF4•Et2O 1–8 10–20 5 5 −1.49 1.32
[Fe2(pdt)(µ-H)(CO)2(dppv)2]+,
[µ-H2]+ 		ClCH2CO2H 2–10 14–40 3.5 3 −1.78 0.95
a

icis the average catalytic current in the plateau region

b

Ecat was calculated at each acid concentration in the linear region by the method described by Fourmond, et al., considering the effects of homoconjugation for the two carboxylic acids.37 The Ecatvalues listed are averages from each acid concentration in the linear region.

c

Overpotential = Eo HA/H2 - Ecat, where EoHA/H2 is the standard reduction potential of the acid.37