S-H bond dissociation enthalpies in thiophenols: A time-resolved photoacoustic calorimetry and quantum chemistry study

被引:69
作者
dos Santos, RMB [1 ]
Muralha, VSF
Correia, CF
Guedes, RC
Cabral, BJC
Simoes, JAM
机构
[1] Univ Lisbon, Fac Ciencias, Dept Quim & Bioquim, P-1749016 Lisbon, Portugal
[2] Univ Lisbon, Ctr Fis, P-1649003 Lisbon, Portugal
[3] Univ Algarve, Fac Engn Recursos Nat, P-8000810 Faro, Portugal
关键词
D O I
10.1021/jp025677i
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Time-resolved photoacoustic calorimetry (TR-PAC) and quantum chemistry calculations were used to investigate the energetics of sulfur-hydrogen bonds in thiophenol and four para-substituted thiophenols, 4-XC6H4SH (X = CH3, OCH3, Cl, and CF3). The result obtained for the PhS-H gas-phase bond dissociation enthalpy, derived from the PAC experimental results in solution, is 349.4 +/- 4.5 kJ mol(-1). This value is significantly higher than recent literature values but agrees with a value suggested some 20 years ago in a widely used review. The PAC result also concurs with the value computed at a high theory level, G3(MP2), 346.8 kJ mol(-1). The data obtained for the substituted thiophenols support the idea that substituent effects are less pronounced on the S-H bond dissociation enthalpy than on the O-H bond dissociation enthalpy of the corresponding phenols.
引用
收藏
页码:9883 / 9889
页数:7
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