The catalytic behaviours of Ruthenium comlex RhC12(TPPTS) 3 as catalyst precursor for the selective hydrogenation of Carbon-crbon double bond in methylvinylketone were studied in biphasic system (aqueous/ cyclohexane ...The catalytic behaviours of Ruthenium comlex RhC12(TPPTS) 3 as catalyst precursor for the selective hydrogenation of Carbon-crbon double bond in methylvinylketone were studied in biphasic system (aqueous/ cyclohexane ). When the hydrogenation was carried out under the following condition: [Ru] = 2 × 10-3mol/L [TPPTS]/[Ru]=3, 2. 0MPa, H2O: 10mL, cyclohexane: 5mL, subettate: 25mmol,stiring speed: 600r/min, the conversion reached 70.13 % and the selectivity for the hydrosenation of C=C was 100%. The effect of molar raio of TPPTS to Ru on the activity was remarkable. When [TPPTS]/[Ru] increased to 15, the conversion raised to 100% and the selectivit was kept unchanged.展开更多
Geometries, harmonic vibrational frequencies and interaction energies of thewater-hydrogen sulfide dimer, hydrogen fluoride dimer and glycine zwitterion-water dimer weredetermined by the counterpoise-corrected (CP-cor...Geometries, harmonic vibrational frequencies and interaction energies of thewater-hydrogen sulfide dimer, hydrogen fluoride dimer and glycine zwitterion-water dimer weredetermined by the counterpoise-corrected (CP-corrected) gradient optimization that explicitlycorrects for the basis set superposition error (BSSE) and CP-uncorrected (normal) gradientoptimization respectively at the B3LYP and MP2 levels of theory, employing the popular Pople'sstandard 6-31G(d), 6-31G(d,p) and 6-311 + + G(d, p) basis sets in order to assess the importance ofCP-corrected gradient optimization in the study of hydrogen bonded systems. The normal optimizationof these three H-bonded systems obtained using these popular basis sets all yielded erratic results,whereas use of CP-corrected gradient optimization led to consistent results with those from largerbasis sets. So this CP receipt becomes useful and necessary to correctly describe large systems,where the use of small basis sets may be necessary.展开更多
A new anionic dinuclear ruthenium complex bearing 1, 2-his(diphenylphosphinomethyl)benzene (BDPX) [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallo-graphic ana...A new anionic dinuclear ruthenium complex bearing 1, 2-his(diphenylphosphinomethyl)benzene (BDPX) [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallo-graphic analysis. This result indicated that complex 1 consisted of an anion dinuclear BDPX-Ru and a cationic di-ethylammonium. The crystal belonged to monoclinic system, C2/c space group with a=3.3552(7) nm, b= 1.8448(4) nm, c=2.4265(5) nm, β= 101.89(3)° and Z=8. The catalytic hydrogenation activities and selectivities of complex 1 for cinnamaldehyde were investigated.展开更多
文摘The catalytic behaviours of Ruthenium comlex RhC12(TPPTS) 3 as catalyst precursor for the selective hydrogenation of Carbon-crbon double bond in methylvinylketone were studied in biphasic system (aqueous/ cyclohexane ). When the hydrogenation was carried out under the following condition: [Ru] = 2 × 10-3mol/L [TPPTS]/[Ru]=3, 2. 0MPa, H2O: 10mL, cyclohexane: 5mL, subettate: 25mmol,stiring speed: 600r/min, the conversion reached 70.13 % and the selectivity for the hydrosenation of C=C was 100%. The effect of molar raio of TPPTS to Ru on the activity was remarkable. When [TPPTS]/[Ru] increased to 15, the conversion raised to 100% and the selectivit was kept unchanged.
基金ProjectsupportedbytheSpecialResearchFoundationofDoctoralEducationofChineseUniversity (No .2 0 0 2 0 610 0 2 4)andtheStrategicGrant (No .70 0 13 5 1)ofCityUniversityofHongKong
文摘Geometries, harmonic vibrational frequencies and interaction energies of thewater-hydrogen sulfide dimer, hydrogen fluoride dimer and glycine zwitterion-water dimer weredetermined by the counterpoise-corrected (CP-corrected) gradient optimization that explicitlycorrects for the basis set superposition error (BSSE) and CP-uncorrected (normal) gradientoptimization respectively at the B3LYP and MP2 levels of theory, employing the popular Pople'sstandard 6-31G(d), 6-31G(d,p) and 6-311 + + G(d, p) basis sets in order to assess the importance ofCP-corrected gradient optimization in the study of hydrogen bonded systems. The normal optimizationof these three H-bonded systems obtained using these popular basis sets all yielded erratic results,whereas use of CP-corrected gradient optimization led to consistent results with those from largerbasis sets. So this CP receipt becomes useful and necessary to correctly describe large systems,where the use of small basis sets may be necessary.
文摘A new anionic dinuclear ruthenium complex bearing 1, 2-his(diphenylphosphinomethyl)benzene (BDPX) [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallo-graphic analysis. This result indicated that complex 1 consisted of an anion dinuclear BDPX-Ru and a cationic di-ethylammonium. The crystal belonged to monoclinic system, C2/c space group with a=3.3552(7) nm, b= 1.8448(4) nm, c=2.4265(5) nm, β= 101.89(3)° and Z=8. The catalytic hydrogenation activities and selectivities of complex 1 for cinnamaldehyde were investigated.
