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a values smaller than 0 as 0 kcal/mol. For data tables, see Supporting Information.
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a of thiols strongly increases with decreasing ε (see Supporting Information, Table S-6). The free-energy profiles for thiols are anticipated to be similar to those for thioethers. Thiols may first react with the Pt(II) complex and become deprotonated subsequently.
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+, calculated at B3LYP/III+//II- in a vacuum (355.9 kcal/mol) is close to the experimental value (356.9 kcal/mol, ref 32) as well as to the reaction energy calculated at CCSD(T)/III+//B3LYP/II- (358.0 kcal/mol).
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2S: -54% (2.36 Å), -27% (2.42 Å), 0% (TS, 2.48 Å, TS).
-
-
-
|