Correction to "electrochemically Determined O-H Bond Dissociation Free Energies of NiO Electrodes Predict Proton-Coupled Electron Transfer Reactivity" (Journal of the American Chemical Society (2019)141: 38 (14971-14975)Doi: 10.1021/jacs.9b07923)

Article abstract of DOI:10.1021/jacs.0c06397

The aqueous CG value used to calculate the bond dissociation free energy (BDFE) values reported in the published Communication was incorrect due to a sign error in its derivation. This systematic error does not affect the conclusions of the study, as all of the aqueous BDFE values shift together. The correct aqueous CG,H2O value is 52.8 kcal mol?1, as reported by Connelly, Wiedner, and Appel.1 We thank Drs. Wiedner and Appel for helpful discussions regarding this correction. We report here revised equations, tables, and schemes with BDFE values adjusted for the correct aqueous CG,H2O term. Pages 14971 and 14972. Equation 1 has been modified to report the correct aqueous CG term, and eqs 4 and 5, which give BDFE values for NiII(OH)2 and NiIIIO(OH), have also been adjusted accordingly. The revised equations are shown below: BDFE(X?H) = 23.06E(pH 0) + 52.8 kcal mol?1 (1) = } =} ? ? Ni O(OH)/Ni (OH) E 0.99 0.03 V BDFE 75.6 1.0 kcal mol III II 2 1 (4) = } = } ? ? Ni O /Ni O(OH) E 1.36 0.02 V BDFE 84.2 1.0 kcal mol IV 2 III 1 (5) Revised BDFE values for the PCET substrates discussed in the original text are given in Table 1. Page 14973. The BDFE ranges discussed in the original publication were adjusted in a similar manner. Thermodynamically favorable reactions at NiIIIO(OH) are predicted for substrates with X?H BDFE less than 75 kcal mol?1 (and were observed for substrates with X?H BDFE ranging from 61 to 73 kcal mol?1). Thermodynamically unfavorable reactivity is predicted (and was observed) for substrates with X?H BDFE greater than 76 kcal mol?1. The observed equilibrium reactivity with 2,4,6-tBu3PhOH is consistent with both the substrate and NiII(OH)2 having an O?H BDFE of ?75.5 kcal mol?1. The number line in Scheme 1 has been adjusted to reflect the corrected BDFE values, and the revised scheme is shown below. [Formula presented] Supporting Information. The BDFE values reported in Tables S1 and S5 were also adjusted for the correct aqueous CG value. The corrected tables are provided in the complete, revised Supporting Information file.

Full text of DOI:10.1021/jacs.0c06397

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Addition/Correction
Correction to “Electrochemically Determined O−H Bond
Dissociation Free Energies of NiO Electrodes Predict Proton-Coupled
Electron Transfer Reactivity”
Catherine F. Wise and James M. Mayer*
J. Am. Chem. Soc. 2019, 141 (38), 14971−14975. DOI: 10.1021/jacs.9b07923
Cite This: https://dx.doi.org/10.1021/jacs.0c06397
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*
sı Supporting Information
III
he aqueous CG value used to calculate the bond
dissociation free energy (BDFE) values reported in the
published Communication was incorrect due to a sign error in
its derivation. This systematic error does not affect the
conclusions of the study, as all of the aqueous BDFE values
cally favorable reactions at Ni O(OH) are predicted for
−
1
T
substrates with X−H BDFE less than 75 kcal mol (and were
observed for substrates with X−H BDFE ranging from 61 to
−
1
73 kcal mol ). Thermodynamically unfavorable reactivity is
predicted (and was observed) for substrates with X−H BDFE
greater than 76 kcal mol . The observed equilibrium reactivity
with 2,4,6- Bu PhOH is consistent with both the substrate and
−1
shift together. The correct aqueous C , value is 52.8 kcal
G H O
2
1
t
−
1
mol , as reported by Connelly, Wiedner, and Appel. We
thank Drs. Wiedner and Appel for helpful discussions
regarding this correction.
3
II
−1
Ni (OH) having an O−H BDFE of ∼75.5 kcal mol .
2
The number line in Scheme 1 has been adjusted to reflect
the corrected BDFE values, and the revised scheme is shown
below.
We report here revised equations, tables, and schemes with
BDFE values adjusted for the correct aqueous CG,H2O term.
Pages 14971 and 14972. Equation 1 has been modified to
III
Scheme 1. Summary of Reactivity at Ni O(OH)
report the correct aqueous C term, and eqs 4 and 5, which
G
II
III
give BDFE values for Ni (OH) and Ni O(OH), have also
2
been adjusted accordingly. The revised equations are shown
below:
BDFE(X−H) = 23.06E(pH 0) + 52.8 kcal mol−1
(1)
(4)
(5)
Ni O(OH)/Ni (OH) E◦ = 0.99 ± 0.03 V
III
II
2
BDFE = 75.6 ± 1.0 kcal mol−
1
Ni O /Ni O(OH) E◦ = 1.36 ± 0.02 V
IV
III
2
BDFE = 84.2 ± 1.0 kcal mol−
1
Supporting Information. The BDFE values reported in
Tables S1 and S5 were also adjusted for the correct aqueous
CG value. The corrected tables are provided in the complete,
Revised BDFE values for the PCET substrates discussed in
the original text are given in Table 1.
Page 14973. The BDFE ranges discussed in the original
publication were adjusted in a similar manner. Thermodynami-
revised Supporting Information file.
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.0c06397.
Table 1. Revised BDFE Values for PCET Substrates
Examined in Reactivity Studies
■
*
a
substrate
BDFE
1
2
,4-hydroquinone
,4,6-tri-tert-butylphenol
68.9
75.5
84.7
86.8
phenol
-acetylphenol
4
a
−1
Aqueous BDFE in kcal mol from ref 2, adjusted for CG,H2O = 52.8
kcal mol− from ref 1. For 1,4-hydroquinone, the reported BDFE is
1
the average for the two O−H bonds.
©
XXXX American Chemical Society
https://dx.doi.org/10.1021/jacs.0c06397
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
A

Journal of the American Chemical Society
pubs.acs.org/JACS
Addition/Correction
Complete experimental details and procedures, charac-
terization of NiO|FTO electrodes, and discussion of data
analysis, including revised BDFE values in Tables S1 and
S5 (PDF)
REFERENCES
■
(
1) Connelly, S. J.; Wiedner, E. S.; Appel, A. M. Predicting the
reactivity of hydride donors in water: thermodynamic constants for
hydrogen. Dalton Trans. 2015, 44, 5933−5938.
(
2) Warren, J. J.; Tronic, T. A.; Mayer, J. M. Thermochemistry of
Proton-Coupled Electron Transfer Reagents and Its Implications.
Chem. Rev. 2010, 110, 6961−7001.
B
https://dx.doi.org/10.1021/jacs.0c06397
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX