143733-27-1Relevant academic research and scientific papers
Direct determination of equilibrium potentials for hydrogen oxidation/production by open circuit potential measurements in acetonitrile
Roberts, John A. S.,Bullock, R. Morris
, p. 3823 - 3835 (2013)
Open circuit potentials were measured for acetonitrile solutions of a variety of acids and their conjugate bases under 1 atm H2. Acids examined were triethylammonium, dimethylformamidium, 2,6-dichloroanilinium, 4-cyanoanilinium, 4-bromoanilinium, and 4-anisidinium salts. These potentials, along with the pKa values of the acids, establish the value of the standard hydrogen electrode (SHE) potential in acetonitrile as -0.028(4) V vs the ferrocenium/ferrocene couple. Dimethylformamidium forms homoconjugates and other aggregates with dimethylformamide; open circuit potentials (OCPs) were used to quantify the extent of these reactions. Overpotentials for electrocatalytic hydrogen production and oxidation were determined from open circuit potentials and voltammograms of acidic or basic catalyst solutions under H2. For these solutions, agreement between OCP values and potentials calculated using the Nernst equation is within 12 mV. Use of the measured equilibrium potential allows direct comparison of catalytic systems in different media; it requires neither pKa values, homoconjugation constants, nor the SHE potential.
Electrochemical reduction of bronsted acids by glassy carbon in acetonitrile-implications for electrocatalytic hydrogen evolution
McCarthy, Brian D.,Martin, Daniel J.,Rountree, Eric S.,Ullman, Alexander C.,Dempsey, Jillian L.
, p. 8350 - 8361 (2014/09/29)
Molecular catalysts for electrochemically driven hydrogen evolution are often studied in acetonitrile with glassy carbon working electrodes and Bronsted acids. Surprisingly, little information is available regarding the potentials at which acids are directly reduced on glassy carbon. This work examines acid electroreduction in acetonitrile on glassy carbon electrodes by cyclic voltammetry. Reduction potentials, spanning a range exceeding 2 V, were found for 20 acids. The addition of 100 mM water was not found to shift the reduction potential of any acid studied, although current enhancement was observed for some acids. The data reported provides a guide for selecting acids to use in electrocatalysis experiments such that direct electrode reduction is avoided.
Free energy landscapes for S-H bonds in Cp*2Mo 2S4 complexes
Appel, Aaron M.,Lee, Suh-Jane,Franz, James A.,DuBois, Daniel L.,Rakowski DuBois, M.
experimental part, p. 5224 - 5232 (2009/09/29)
An extensive family of thermochemical data is presented for a series of complexes derived from Cp*Mo(μ-S)2(μ-SMe)(μ-SH)MoCp * and Cp*Mo(μ-S)2(μ-SH)2MoCp*. These data include electrochemical potentials, pKa value
Addition of Anilines to the BF4 Complex, and the 'Ordered Transition State Mechanism'
Odiaka, Timothy I.
, p. 561 - 566 (2007/10/02)
Kinetic studies of the reversible addition of anilines to the complex BF4 (1;dienyl=C7H9) have demonstrated the dependence of rate on the electronic and steric nature of the attacking nucleophile.A plot of ΔHa versus ΔSa for the reaction of aniline with the complexes BF4 (1; dienyl=C6H7, 2-MeOC6H6, or C7H9) is linear,the slope of which gives an isokinetic temperature of 369 +/- 23 K, indicating enthalpy control over the associative process.The reaction of aniline and other substituted anilines with complexes (1) clearly reveals the predominance of negative entropies of activation for the dissociative processes in these systems, thus providing strong support for the recently proposed 'Ordered Transition State Mechanism'.
