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• W2044552316 abstract "We have prepared the dimer radical cations (R2S)2+· of a series of dialkyl sulfides R2S (= Me2S, MeEtS, Et2S, Et-n-PrS, n-Pr2S, i-Pr2S, n-Bu2S) in an FT-ICR cell. These have been found to react with neutral dialkyl sulfides by ligand exchange. By studying the (R2S)2+· + 2Et2S ⇄ (Et2S)2+· + 2 R2S equilibria the associated Gibbs energy changes ΔG0 have been determined. From these, the sulfur–sulfur bond dissociation enthalpies (BDE) of the dimers could be estimated using the relationship BDE[(R2S)2+·] = −ΔG0 − TΔS0 + IE[Et2S] − IE[R2S] + BDE[Et2S)2+·] and taking literature values for BDE[(Et2S)2+·] and the ionization energies IE[R2S]. The entropies of reaction ΔS0 have been estimated using statistical thermodynamics and computationally optimized structures. The 298 K sulfur–sulfur BDE values thus obtained are 115, 112, 115, 107, 103, and 97 kJ mol−1 for (Me2S)2+·, (MeEtS)2+·, (Et2S)2+·, (Et-n-PrS)2+·, (n-Pr2S)2+· and (n-Bu2S)2+·, respectively. The trend in S–S bond strength as well as the various contributions to ΔS0 are discussed." @default.
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• W2044552316 date "1998-11-01" @default.
• W2044552316 modified "2023-09-23" @default.
• W2044552316 title "Sulfur–sulfur three-electron bond dissociation enthalpies of dialkyl sulfide dimer radical cations" @default.
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• W2044552316 doi "https://doi.org/10.1016/s1387-3806(98)14072-1" @default.
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