Erratum: Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities (Journal of the American Chemical Society (2019) 141:38 (15230-15239) DOI: 10.1021/jacs.9b07062)

Article abstract of DOI:10.1021/jacs.0c09331

Pages 15232, 15233, and 15236. In the original paper, the doublet wave functions for 21 and 21a/21b were incorrectly (Figure Presented). reported as spin-contaminated in sections 2.3 and 2.8 (Figure 3 and Scheme 9, respectively.) This comes from the incorrectly reported expected eigenvalue of 0.75 for the spin-squared operator ??2? for the antiferromagnetically coupled doublet |↓?L|↑↑?V state (originally given in the Supporting Information). The correct expected eigenvalue for the |↓?L|↑↑?V state should be 1.75. The wave functions for 21 and 21a/21b (eigenvalues 1.79 and 1.77/1.66, respectively) are therefore not spincontaminated. The corrected Figure 3 and Scheme 9 are presented below. A corrected Supporting Information file is also provided. The corrections do not affect any of the conclusions of the Article, but slightly decrease the gap between the quartet and doublet spin surfaces. Scheme 3 has been also corrected to reflect the fact that (CH3)3SiCH2 ? radicals can only react based on spin conservation.

Full text of DOI:10.1021/jacs.0c09331

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Addition/Correction
Correction to “Redox-Noninnocent Ligand-Supported Vanadium
Catalysts for the Chemoselective Reduction of CX (X = O, N)
Functionalities”
Guoqi Zhang,* Jing Wu, Shengping Zheng, Michelle C. Neary, Jincheng Mao,* Marco Flores,
Ryan J. Trovitch, and Pavel A. Dub*
J. Am. Chem. Soc. 2019, 141 (38), 15230−15239. DOI: 10.1021/jacs.9b07062
Cite This: https://dx.doi.org/10.1021/jacs.0c09331
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Supporting Information
ACCESS
Pages 15232, 15233, and 15236. In the original paper, the
|↓⟩L|↑↑⟩V state (originally given in the Supporting Information).
The correct expected eigenvalue for the |↓⟩L|↑↑⟩V state should
2
2
doublet wave functions for 1 and 1a/21b were incorrectly
2
2
be 1.75. The wave functions for 1 and 1a/21b (eigenvalues
1.79 and 1.77/1.66, respectively) are therefore not spin-
contaminated.
The corrected Figure 3 and Scheme 9 are presented below. A
corrected Supporting Information file is also provided. The
corrections do not affect any of the conclusions of the Article,
but slightly decrease the gap between the quartet and doublet
spin surfaces. Scheme 3 has been also corrected to reflect the fact
•
that (CH3)3SiCH2 radicals can only react based on spin
conservation.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.0c09331.
■
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Detailed experimental procedures, characterization data,
X-ray crystallographic data, and computational details
(corrected) (PDF)
Figure 3. Influence of different UDFT/SMD(Et2O) functionals/basis
sets on the energy difference between the doublet and quartet spin
states for 1. Mulliken spin density plots (yellow, α-spin; blue, β-spin)
2
̂
and calculated eigenvalues of the spin-squared operator ⟨S ⟩ are given
for the quartet and doublet of 1 optimized at the ωB97XD/def2-SVP
level; noncritical H atoms are omitted for clarity. The ideal eigenvalues
2
̂
of ⟨S ⟩ are 3.75 (|↑⟩L|↑↑⟩V state) and 1.75 (|↓⟩L|↑↑⟩V state),
respectively.
reported as spin-contaminated in sections 2.3 and 2.8 (Figure 3
and Scheme 9, respectively.) This comes from the incorrectly
reported expected eigenvalue of 0.75 for the spin-squared
2
̂
operator ⟨S ⟩ for the antiferromagnetically coupled doublet
https://dx.doi.org/10.1021/jacs.0c09331
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© XXXX American Chemical Society
A

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Addition/Correction
Scheme 3. Reaction Profile Leading to 41 + (CH3)4Si + LiH vs 44 + (CH3)3SiCH2CH2Si(CH3)3 Computed at the ωB97XD/def2-
a
SVP/SMD(diethyl ether) Level
a
Mulliken spin density plots (yellow, α-spin; blue, β-spin) are shown for selected stationary points; noncritical H atoms are omitted for clarity.
B
https://dx.doi.org/10.1021/jacs.0c09331
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Addition/Correction
Scheme 9. (A) Experimental Reactions between 1/1H or 2
with 2.2 equiv of HBpin or PhSiH3 and (B) ωB97X-D/def2-
SVP/SMD(Et2O) Thermodynamics of the Reactions 41 → 1a
a
→ 1b
a
ΔG°298 K values are given in kcal·mol−1 (1 M).
C
https://dx.doi.org/10.1021/jacs.0c09331
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX