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Title: The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of ortho-12-Carborane

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [2];  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Czech Academy of Sciences, Prague (Czech Republic)
  3. Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences, Prague (Czech Republic)
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A massive structural change accompanies electron capture by the 1,2-dicarba-closo-dodecaborane cage molecule (1). Bimolecular electron transfer (ET) by pulse radiolysis found a reduction potential of E0 = –1.92 V vs Fc+/0 for 1 and rate constants that slowed greatly for ET to or from 1 when the redox partner had a potential near this E0. Moreover, two electrochemical techniques could detect no current at potentials near E0, finding instead peaks or polarographic waves near –3.1 V, which is 1.2 V more negative than E0. Voltammetry could determine rate constants, but only near –3.1 V. DigiSim simulations can describe the irreversible voltammograms but require electrochemical rate constants near 1 × 10–10 cm/s at E0, a factor of 10–10 relative to molecules undergoing facile ET. This factor of 10–10 compared to ~10–5 for bimolecular ET introduces a puzzle. This puzzle can be understood as a manifestation of one of the “Frumkin Effects” in which only part of the applied voltage is available to drive ET at the electrode.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1572367
Report Number(s):
BNL-212237-2019-JAAM; TRN: US2001322
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 123, Issue 45; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

References (26)

On the Theory of Electron‐Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions journal July 1965
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I journal May 1956
Reorganization Energy of the Initial Electron-Transfer Step in Photosynthetic Bacterial Reaction Centers journal January 1998
A photoelectron spectroscopic and computational study of the o -dicarbadodecaborane parent anion journal June 2016
Electron-Transfer Reactions with Significant Inner Reorganization Energies. Two-Electron Oxidation of Derivatives of 1,4-Bis(dialkylamino)-1,3-butadiene journal January 1996
Electron-Transfer Reactions with Significant Changes in Structure. Unsymmetrical Crowded Ethylenes journal December 2006
Kinetics of Multielectron Transfers and Redox-Induced Structural Changes in N -Aryl-Expanded Pyridiniums: Establishing Their Unusual, Versatile Electrophoric Activity journal August 2015
Indirect Determination of Self-Exchange Electron Transfer Rate Constants journal August 1998
Self-exchange reactions of cobalt complexes and implications concerning redox reactivity of vitamin B12 journal January 1972
Comparison of proton- and electron-transfer equilibriums and rates for tetraalkylhydrazines journal December 1981
Examination of the intrinsic barrier to electron transfer in hexaaquacobalt(III): evidence for very slow outer-sphere self-exchange resulting from contributions of Franck-Condon and electronic terms journal June 1982
Mechanism of Cobalt Self-Exchange Electron Transfer journal September 2013
A Camouflagednido-Carborane Anion: Facile Synthesis of Octa-B-methyl-1,2-dicarba-closo-dodecaborane(12) and Its Deboration Reaction journal April 1999
The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory journal November 2004
Evidence for a two-step electron-transfer process in the electrode reactions of tetraisopropylhydrazine, tetracyclohexylhydrazine and their radical cation salts journal May 2000
Free Energy and Temperature Dependence of Electron Transfer at the Metal-Electrolyte Interface journal February 1991
The transfer of electrons in the carborane series journal October 1970
1,2-Dehydro-o-carborane journal May 1990
New methods for the accurate determination of extinction and diffusion coefficients of aromatic and heteroaromatic radical anions in N,N-dimethylformamide journal August 1998
On the theory of electron transfer reactions. The naphthalene−·/TCNQ system journal November 1977
Effect of free energy on rates of electron transfer between molecules journal September 1984
Theory of highly exothermic electron transfer reactions journal March 1982
Theoretical Treatment of the Kinetics of Diffusion-Limited Reactions journal July 1957
Estimation of inner shell Marcus terms for amino nitrogen compounds by molecular orbital calculations journal February 1987
p -Carborane Conjugation in Radical Anions of Cage–Cage and Cage–Phenyl Compounds journal January 2018
Wasserstoffüberspannung und Struktur der Doppelschicht journal January 1933

Figures / Tables (24)

Figure 1(p. 5)figure Figure 1
Chart 1(p. 6)figure Chart 1
Figure 2(p. 8)figure Figure 2
Figure 3(p. 11)figure Figure 3
Figure 4(p. 13)figure Figure 4
Figure 5(p. 15)figure Figure 5
Figure 6(p. 15)figure Figure 6
Figure 7(p. 16)figure Figure 7
Figure 8(p. 17)figure Figure 8
Figure 9(p. 18)figure Figure 9
Table 1(p. 20)table Table 1
Figure 10(p. 26)figure Figure 10
Figure S1(p. 34)figure Figure S1
Figure S2(p. 36)figure Figure S2
Figure S3(p. 37)figure Figure S3
Figure S4(p. 38)figure Figure S4
Figure S5(p. 39)figure Figure S5
Figure S6(p. 39)figure Figure S6
Figure S7(p. 40)figure Figure S7
Table S1(p. 41)table Table S1
Figure S8(p. 42)figure Figure S8
Figure S9(p. 42)figure Figure S9
Figure S10(p. 43)figure Figure S10
Figure S11(p. 44)figure Figure S11

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Related Subjects

14 SOLAR ENERGY
Homogeneous vs heterogeneous electron transfer
reorganization energy
cyclic voltammetry
pulse radiolysis
overpotential
Frumkin Effect
free energy relation
carborane