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- Since many dihydrogen complexes also form dinitrogen complexes, it is advisable to employ an argon or helium atmosphere instead of the usual dinitrogen deaeration.
- irreversible. We gratefully accept the referee's suggestion to make clear, to the readers less expert in electrochemical things, the implications underlying the term. It is used here simply to put in evidence the lack of any directly associated response in the reverse scan of the cyclic voltammograms, as it is in use in inorganic electrochemistry. In a strict electrochemical sense, the term refers to non-nerstian electron transfers, which manifest responses, the potentials of which are destitute of thermodynamic significance. Nevertheless, in most of the electrochemical responses displayed by organometallic species, the lack of backward responses is caused by chemical complications quickly consuming the primarily electrogenerated species, rather than by very slow electron exchanges. Under these assumptions, we attribute an acceptably approximate thermodynamic meaning to the peak potential values of the redox changes discussed here, the apparent irreversibility of which is generally due to fast proton or dihydrogen losses.
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- We have recently experienced that Coulombic effects can induce shifts in redox potentials of closely related species ranging from 0.7 V to 1 V.10, 31
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- The nearly crossing tracks in the reverse scan of Fig. 12 (as well as that in Fig. 6) are indicative of the occurrence of complex reaction pathways at the electrade surface. One likely reaction following the electron removal is the loss of dihydrogen, which is in turn oxidized to H+ at the positive working potentials.
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- Comparisons between redox potentials are valid if allowance is made to think that they depend to a higher extent on the oxidation state of the metal than on the geometry of the complexes.
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