The oxidation of thiophenol（RSH） to phenyl disulfide catalyzed by Co（Ⅱ） tetrakis（propyl-oxycarbonyl）phthalocyanine[CoPc（COOC3H7）4] in the presence of molecular oxygen was studied in synthetic bilayer membrane...The oxidation of thiophenol（RSH） to phenyl disulfide catalyzed by Co（Ⅱ） tetrakis（propyl-oxycarbonyl）phthalocyanine[CoPc（COOC3H7）4] in the presence of molecular oxygen was studied in synthetic bilayer membrane of vesicle, which is composed of hexadecyl 2-hydroxy-3-chloropropyl phosphate, SDS micelle, ethanol and benzene respectively. The catalytic activities followed the order of \{CoPc（COOC\}3H7）4 in the bilayer membrane>ethanol>benzene, and in the bilayer membraneSDS micelle. UV-Vis spectroscopic studies reveal that the catalytic oxidation proceeds through RS--CoPc-O2 intermediate. The catalytic activity of CoPc（COOC3H7）4 in the bilayer membrane of vesicle higher than that in the other media is considered to be attributable to the disaggregation of CoPc（COOC3H7）4 incorporated into the bilayer membrane and the easier H+ dissociation of RSH on the polar surface of the bilayer membrane bordered by bulk aqueous phase.展开更多
由于煤氧化反应的初始阶段就是煤吸附O2的过程,可通过抑制O2的吸附来抑制煤的氧化自燃。应用Gaussian 03程序,采用密度泛函(DFT)方法,在B3LYP/6-31G(d,p)水平下研究分析Zn2+与煤中α位硫酚结构的作用机理,并以活化能作为指标表征Zn2+抑...由于煤氧化反应的初始阶段就是煤吸附O2的过程,可通过抑制O2的吸附来抑制煤的氧化自燃。应用Gaussian 03程序,采用密度泛函(DFT)方法,在B3LYP/6-31G(d,p)水平下研究分析Zn2+与煤中α位硫酚结构的作用机理,并以活化能作为指标表征Zn2+抑控煤中α位硫酚结构氧化的效果。由计算结果可知,α-萘硫酚结构中S原子LP(2)轨道上的孤对电子向Zn的LP*(6)空轨道转移,通过sp杂化形成σZn-S配位键,配位键的二阶稳定化能为266.60 k J/mol。当α-萘硫酚结构氧化时,首先与O2发生物理吸附形成复合物ComplexⅠ并释放20.12 k J/mol的能量,然后复合物ComplexⅠ的分子间发生化学作用,导致O2分子被化学吸附在—SH基上,所需活化能Ea=62.71k J/mol。[Zn SH8C10]2+配合物物理吸附O2释放的能量减少了14.92 k J/mol,且形成化学吸附所需的活化能增加了47.62 k J/mol,Zn2+对煤中α位硫酚氧化具有明显的控制作用。展开更多
在B3LYP/6-311+G(d,p)水平上研究了2-(1H-咪唑)苯硫酚(1d)、2-(噁唑)苯硫酚(2d)、2-(噻唑)苯硫酚(3d)及其衍生物的基态质子转移过程,探讨取代基电子效应对质子转移的影响.结果表明:吸电子引入后分子平面电子密度减小,N2-H1间距减小,分...在B3LYP/6-311+G(d,p)水平上研究了2-(1H-咪唑)苯硫酚(1d)、2-(噁唑)苯硫酚(2d)、2-(噻唑)苯硫酚(3d)及其衍生物的基态质子转移过程,探讨取代基电子效应对质子转移的影响.结果表明:吸电子引入后分子平面电子密度减小,N2-H1间距减小,分子内氢键增强,醇式到酮式质子转移能垒减小;供电子基引入后分子平面电子密度增大,N2-H1间距增大,分子内氢键减弱,质子转移能垒增大.Localized orbital locator(LOL)分析表明:取代基的引入对N1原子成键性质产生影响明显.三者质子转移能垒大小为1d<3d<2d,取代基引后能垒相对大小不变.展开更多
The method of Michael addition reaction of thiophenol with intramolecular hydrogen bond in an aqueous medium was reported. The aqueous reactive medium includes saturated sodium bicarbonate solution and catalytic amoun...The method of Michael addition reaction of thiophenol with intramolecular hydrogen bond in an aqueous medium was reported. The aqueous reactive medium includes saturated sodium bicarbonate solution and catalytic amount of tetrabutylammonium bisulfate. 2-Hydroxythiophenol,2-aminothiophenol,2-carboxythiophenol,ethyl acrylate and arcylonitrile were selected as model molecules to demonstrate the method. It is found that the reaction can be accomplished rapidly at room temperature with a high yield,and no mercapto-coupling byproduct formed.展开更多
文摘The oxidation of thiophenol（RSH） to phenyl disulfide catalyzed by Co（Ⅱ） tetrakis（propyl-oxycarbonyl）phthalocyanine[CoPc（COOC3H7）4] in the presence of molecular oxygen was studied in synthetic bilayer membrane of vesicle, which is composed of hexadecyl 2-hydroxy-3-chloropropyl phosphate, SDS micelle, ethanol and benzene respectively. The catalytic activities followed the order of \{CoPc（COOC\}3H7）4 in the bilayer membrane>ethanol>benzene, and in the bilayer membraneSDS micelle. UV-Vis spectroscopic studies reveal that the catalytic oxidation proceeds through RS--CoPc-O2 intermediate. The catalytic activity of CoPc（COOC3H7）4 in the bilayer membrane of vesicle higher than that in the other media is considered to be attributable to the disaggregation of CoPc（COOC3H7）4 incorporated into the bilayer membrane and the easier H+ dissociation of RSH on the polar surface of the bilayer membrane bordered by bulk aqueous phase.
文摘由于煤氧化反应的初始阶段就是煤吸附O2的过程,可通过抑制O2的吸附来抑制煤的氧化自燃。应用Gaussian 03程序,采用密度泛函(DFT)方法,在B3LYP/6-31G(d,p)水平下研究分析Zn2+与煤中α位硫酚结构的作用机理,并以活化能作为指标表征Zn2+抑控煤中α位硫酚结构氧化的效果。由计算结果可知,α-萘硫酚结构中S原子LP(2)轨道上的孤对电子向Zn的LP*(6)空轨道转移,通过sp杂化形成σZn-S配位键,配位键的二阶稳定化能为266.60 k J/mol。当α-萘硫酚结构氧化时,首先与O2发生物理吸附形成复合物ComplexⅠ并释放20.12 k J/mol的能量,然后复合物ComplexⅠ的分子间发生化学作用,导致O2分子被化学吸附在—SH基上,所需活化能Ea=62.71k J/mol。[Zn SH8C10]2+配合物物理吸附O2释放的能量减少了14.92 k J/mol,且形成化学吸附所需的活化能增加了47.62 k J/mol,Zn2+对煤中α位硫酚氧化具有明显的控制作用。
文摘在B3LYP/6-311+G(d,p)水平上研究了2-(1H-咪唑)苯硫酚(1d)、2-(噁唑)苯硫酚(2d)、2-(噻唑)苯硫酚(3d)及其衍生物的基态质子转移过程,探讨取代基电子效应对质子转移的影响.结果表明:吸电子引入后分子平面电子密度减小,N2-H1间距减小,分子内氢键增强,醇式到酮式质子转移能垒减小;供电子基引入后分子平面电子密度增大,N2-H1间距增大,分子内氢键减弱,质子转移能垒增大.Localized orbital locator(LOL)分析表明:取代基的引入对N1原子成键性质产生影响明显.三者质子转移能垒大小为1d<3d<2d,取代基引后能垒相对大小不变.
文摘The method of Michael addition reaction of thiophenol with intramolecular hydrogen bond in an aqueous medium was reported. The aqueous reactive medium includes saturated sodium bicarbonate solution and catalytic amount of tetrabutylammonium bisulfate. 2-Hydroxythiophenol,2-aminothiophenol,2-carboxythiophenol,ethyl acrylate and arcylonitrile were selected as model molecules to demonstrate the method. It is found that the reaction can be accomplished rapidly at room temperature with a high yield,and no mercapto-coupling byproduct formed.
