简介:采用CBS-QB3方法构建了丙烯酸甲酯(CH_2=CHCOOCH_3)与O_3反应体系的势能剖面并在此基础上利用经典过渡态理论(TST)和Wigner矫正模型计算了标题反应在200K~1200K温度区间内的速率常数kTST/W.研究结果表明,CH_2=CHCOOCH)3与O)3反应首先经过渡态生成一个稳定的五元环中间体,然后按断键位置不同,分别生成产物P1(CH_3OCOCHO+CH_2O_2)和P2(CH)3OCOCHOO+HCHO).此外,速率常数结果显示,在计算温度范围内,标题反应速率常数呈正温度系数效应.294K时,CH_2=CHCOOCH_3与O_3反应速率常数为1.76×10^(-18)cm^3·molecule^(-1)·s^(-1),与所测实验值(0.95±0.07)×10^(-18)cm^3·molecule^(-1)·s^(-1)非常接近.
简介:Halfsandwichirondicarbonylcomplex[η5-C5H3(t-Bu)2]Fe(CO)2Cl(1)reactswith1,2-dilithiumdiselenocarboraneLi2Se2C2B10H10(2)togiveabinuclearironcarboranecomplex[η5-C5H3(t-Bu)2]2Fe2(CO)3*Se2C2B10H10(3).TheX-raydiffractionanalysisofcomplex3revealsthatoneoftheironatomsischiral.
简介:利用水热技术合成了一个以Keggin型多金属氧酸盐和柔性有机配体为建筑块的三维超分子化合物[H2bbi]3[α-PMo12O40]2(1)(bbi=1,4-双-(咪唑-1-基)丁烷),用X-射线单晶衍射、元素分析、红外光谱和X-射线粉末衍射对晶体结构进行了表征.X-射线单晶衍射显示,该晶体属于三斜晶系,P-1空间群,a=1.18360(9)nm,b=1.20932(10)nm,c=1.77728(15)nm,α=74.0890(10)°,β=70.9490(10)°,γ=71.8160(10)°,V=2.2421(3)nm3,Z=2,Dc=3.109g/cm3,F(000)=2300,μ=3.39mm-1,S=1.047,R1=0.0350,wR2=0.0776[I〉2σ(I)].
简介:TostudytheintramolecularDiels-Aldercycloadditonof2H-chromen-2-oneasadiene,aseriesofchiralN-allyl-N-benzylamidesthatcontaina2H-chromen-2-onemoietyweredesignedforthesynthesisofbenzo[f]isoindol-l-onesviaanintramolecularDiels-Alderandasubsequentretro-Diels-AldercycloadditionwiththeexpulsionofCO2.Boththeyield(80%-89%)andabsolutestereocontrolofthetandemreactionwerehighwhenanelectron-withdrawinggroupwasattachedtothedienophile.Thedoublebondinthestyrenesubstructureremainedintheproductscouldbefurtherderivatizedbydihydroxylation.
简介:Three-dimensional(3D)flowerlikehierarchicalZn2GeO4andMn2+-dopedZn2GeO4microstructureshavebeenpreparedbyafacilehydrothermalapproach.X-Raydiffraction(XRD),fieldemissionscanningelectronmicro-scopy(FESEM),transmissionelectronmicroscopy(TEM)andphotoluminescence(PL)spectrometrywereemployedtocharacterizethesamples.SuchflowerlikehierarchicalZn2GeO4microstructureswithanaveragediameterof3―4μmwerefoundtobeconstructedbyabundantsinglecrystallinenanorodsofabout90nmindiameter.TheluminescentpropertiesofZn2GeO4:xMnphosphorswithdifferentcontentsofMn2+asanactivatorwereinvestigated.TheMn2+-dopedsamplesshowedgreenluminescencecorrespondingtothed-dtransitionofMn2+undertheirradiationofUVlight.Theredshift(from531nmto538nm)inλemwithincreasingMn2+contentwasobservedintheluminescentspectra,whichshouldbeattributedtoaweakcrystalfieldbecauseofthesubstitutionofZn2+byMn2+atadistortedtetrahedrallatticesite.
简介:Aseriesofnovel1H-benzimidazol-1-ylacetatesand1H-benzimidazol-1-ylpropionatescontaining1H-1,2,4-triazolemoietyweresynthesizedundermicrowaveirradiationbymulti-stepreactions,inyieldsof87-94%.TheirinvitroantifungalactivitiesagainstBotrytiscinereaandSclerotiniasclerotiorumwereevaluatedbymycelialgrowthratemethod.AllthetargetcompoundsexhibithighactivitiesagainstB.cinereawiththeEC50valuesof7.96-21.74μg/mL,higherthanthatofcarbendazim.
简介:AseriesofTiO2-XSiO2[Xdenotesthemolarfraction(%)ofsilicainthemixedoxides]withdifferentn(Ti)/n(Si)ratioswaspreparedwithammoniawaterasahydrolysiscatalyst.ThephotocatalystspreparedwerecharacterizedbyXRD,thermalanalysis,FTIR,UV-VisandSPS.ThecharacterizationresultsofFTIRandUV-VisspectrashowthatTiatomsweregraduallychangedfromoctahedralcoordinationtotetrahedralcoordinationwiththeadditionofsilica,whichisnotbeneficialforobtainingstrongBrnstedacidityandhigherphotocatalyticactivity.Thephotocatalyticactivityexperiments,whichwereconductedbyusingheptane(orSO2)asthemodelreactant,showedthatTiO2-SiO2containingasuitableamountofsilicacanexhibitmuchhigherphotocatalyticactivitythanpureTiO2.Theenhancedphotocatalyticactivitycanbeattributedtothreefollowingfactors:(1)smallercrystallinesize;(2)higherthermalstability;(3)thenewstrongBrnstedacidity.
简介:CarbonylationofAllylChlorideCatalyzedbyPdCl2(TPPTS)2inTwo-phaseMediumCarbonylationofAllylChlorideCatalyzedbyPdCl2(TPPTS)2in...
简介:ElectrolyticfixationofCO2wasinvestigatedbyelectrocarboxylationoforganichalides(RX),andfourestersⅠ,ⅡⅢ,Ⅳ)wereobtainedinmoderateyields.ElectrochemicalreductionesterificationsofRXinthepresenceofCO2werecarriedoutonnanocry'stallineTiO2-Ptelectrode.TheelectrochemicalbehaviorofRXinthepresenceofCO2wasinvestigatedbythetechniqueofcyclicvoltammetry,andtheprobablereactionmechanismw,asproposed.
简介:Emissionquenchingof[Ru(bpy)2(4,4’-dcbpy)](PF6)2(1)bybenzenamine,4-[2-[5-[4-[4-dimethylamino]phenyl]-4,5-di-hydro-1-phenyl-1H-pyrazol-3-yl]-ethenyl]-N,N-dimetyl(2)or1,5-diphenyl-3-(2-phenothiazine)-2-pyrazoline(3)wasobserved.Measurementsoftheemissiondecayof1beforeandafteradditionof2or3bysinglephotoncountingtechniquecon-finnedtheobservations.Theemissionquenchingof1by2or3wassubmittedtoStern-Volmerequation.Itwascalculatedthatthequenchingrateconstants(kq)are5.5×109(mol/L)-1s-1for2and4.0×109(mol/L)-1s-1for3,respectively.Theseresultsindicatedacharacterofdynamicquenchingprocess.Thesinglet-stateof2or3wasalsoquenchedby1.ThequenchingbehaviorsdidnotconformtotheStern-Volmerequationandinvolvedbothstaticanddynamicquenchingprocesses.Theapparentquenchingrateconstant(kapp)wascalculatedtobe3×109(mol/L)-1fortheinteractionofexcited2with1,and1.2×109(mol/L)-1forthatofexcited3wit
简介:WiththedecreaseofpHvaluefrom8.45to–1.0,theUV-Visabsorptionandfluorescentspectraof1,2-bis(4-pyridyl)ethylene(BPE)tookonthesamechangingtrendatfourdifferentsuccessivepHstages:8.45―7.20,7.20―5.62,5.62―2.60,and2.60―-1.0,namely,nochange,decrease,increase,anddecreaseagain.Amongthese,inarangeof7.20―5.62,thefluorescencewavelengthblueshiftedfrom418to359nm,buttheUV-Visabsorptionwavelength,incontrast,redshiftedfrom285to298nm.ThefluorescenceintensityofBPEhadadropeventoquenchuponadeclineinthepHvaluefrom2.60to–1.0probablyowingtoitscation-πinteractiontoreducetheπelectronclouddensityofBPE.Twodissociationconstants,pKa1(4.30±0.01)andpKa2(5.65±0.04),wereobtainedbasedonfluorescencedata.ThechangesoffluorescencespectraindicatethatBPEhas'off-on-off'switchbehavior.ThefluorescentspectraofBPEwerenearlyindependentonthepresenceofα-andβ-cyclodextrins.
简介:Directasymmetricaldoladditionofmethylketonesto2,2,2-trifluoro-1-phenylethanoneanditsring-substitutedderivativeswasachievedusingL-prolineasachiralpromoter.Variousopticallyactiveβ-trifluoromethyl-β-hydroxyketoneswereobtainedinalmostquantitativeyieldswithmoderateenantioselectivitiesupto64%ee.