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mized geometries. Free energies include unscaled free energy correc-
tions from M06–2X/def2-SVP computations and solvation corrections
(in implicit THF) from COSMO-RS (at the PBE0-dDsC/TZ2P level). Elec-
tronic energies obtained with M06-2X/def2-TZVP: with thiophenolate
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[35] All reactions were carried out following standard prudent practices in
the laboratory. See for example: Prudent Practices in the Laboratory:
Handling and Management of Chemical Hazards, Updated Edition, Na-
tional Research Council of the National Academies, The National Acade-
my Press, Washington, DC, 2011.
(13b’): 11.2 kcalmolÀ1; with thiophenol radical (13b’’): 12.0 kcalmolÀ1
;
with thiophenol: 42.9 kcalmolÀ1. See the Supporting Information for
further details.
[22] Examination of the intrinsic reaction coordinate (IRC) further supported
the concerted nature of the proposed mechanism. See the Supporting
Information for selected IRC structures.
[23] Electronic energies obtained with M06-2X/def2-TZVP: 17.9 kcalmolÀ1
See the Supporting Information for further details.
.
[24] At this stage, the exact mechanism of the conversion of disulfides to
thiocyanates is unknown and will be the topic of future studies.
[25] The same computational methods were used as in ref. [20], conse-
quently the technical section is reprinted (adapted) with permission
from J. Am. Chem. Soc. 2014, 136, 16563, copyright 2014 American
Chemical Society.
Received: November 21, 2014
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Published online on && &&, 0000
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