简介:Asymmetrichydrisilylationcatalyzedbypolymericthiazolidinerhodiumcatalystswasconducted.Almostthesameopticalyieldshavebeenobtainedwhencomb-shapedpolymericligandsandtheircorrespondingmonomercomplexedrhodiumcataltystswereusedtoasymmetrichydrosilylationofacetophenone.Opticalyieldofchiral1-methylbenzylalcoholreachesashighas71.5%.Temperaturedependenceofenantioselectivehydrosilylationofacetophenonewasdiscussed.
简介:AC2-symmetricalaryldiphosphitederivedfromchiralbinaphtholwaspreparedanditsrhodiumcomplexwasusedascatalystsintheasymmetrichydroformylationofolefins.Highcatalyticactivityandgoodregioselectivitywereobserved.Upto31.2%eeand38.1%eewereachievedforthehydroformylationof4-fluoro-styreneandvinylacetaterespectively.Theinfluencesofligand-to-metalratio,reactiontemperatureandthepressureofsyn-gasontheenantioselectivityandregioselectivitywerealsostudied.
简介:Twokindsofrhodiumcatalystssupportedoncross-linkedstyrene-divinylbenzenecopolymerscontainingbipyridineoro-phenylenediaminehavebeenpreparedandfoundtodisplayhighactivityformethylacetatecarbonylationtoformaceticanhydride,theactivitiesareevenhigherthantheirhomogeneouscounterparts.XPSanalysiswasusedtocharacterizethesyntheticcatalysts.TheapparentactivationparametersweredeterminedtobeEα=73.3KJ/mol,ΔH^≠=66.3KJ/mol,ΔS^≠=-28.6eu.Theseparametersareveryclosetothoseinmethanolcarbonylationandimplytohaveanalogousmechanisminbothcases.
简介:Silica-boundmercaptoselenaether-containingsilsesquioxaneanditsplat-inumorrhodiumcomplexweresynthesizedfromγ-(2,3-epithiopropyl)propyltrimethoxysi-laneviaring-openingreactionwithbis(2-hydroxyethyl)sclenide,followedbyhydrolysisandimmobilizationonfumedsilica,andthenreactingwithpotassiumchloroplatiniteorrhodiumchlorideinacetoneundernitrogenatmosphere.Itwasfoundthattwonoblemetalcomplexescancatalyzethehydrosilylationofolefinswithtriethoxysilaneeffectively.Theinfluencesoftemperature,theamountofcomplexused,thenatureofolefinoncatalyticactivitywereinvestigated.
简介:Aseriesofpolymer-supportedtetranuclearrhodiumcarbonylclustercatalystswerepreparedbthereactionofRh4(CO)12withseveralkindsofpolymersupportssuchascrosslinkedpoly(N-vinylpyrrolidone)(PNVP)andcrosslinkedpoly(styrene-co-maleicanhydride)(PMAn),andsubsequentlywereusedtocatalyzethehydroformylationofolefins.ThecatalystswerecharacterizedbyIR,SEMandXPS.Theinfluenceofthesupportsstructureandcrosslinking,metal’scontentandparticlesizeofthesupportsonthecatalystshydroformylationpropertieswasstudied.Thefactorswhichaffectthecatalyticconversionwerealsoexamined.Theexperimentalresultsshowthatthepolymer-supportedRhclustercatalystspossessveryhighcatalyticactivityandaldehydeselectivityaswellasgoodreproducibility.
简介:CATALYTIC PROPERTIES OF SILICA-SUPPORTED POLY-γ-AMINOPROPYLSILOXANE-RHODIUM-COBALT BIMETALLIC COMPLEX FOR HYDROFORMYLATIONCAT...
简介:LocalstructuresofthemolybdenumsulfidespeciesinthesultidedRh-Mo-K/Al2O3catalystswithvariousrhodiumloadingshavebeeninvestigatedbyXAFS.Fromthefittingresults.theMo-Mocoordinationnumberforthesamplefreeofrhodium(ca.3.7)issimilartothatforthecrystallineMoS2,indicatingthatthesupportedsulfidedmolybdenumspeciesmainlypresentaslargepatechesofMoS2-likeslabs.Fortherhodium-modifiedsamples,however,theamplitudesoftheMo-SandMo-Mocoordinationshellsaresharplyreduced,revealingahighdispersionoftheMoS2-likespeciesinthecatalysts,TheschemeofthemicrostructuresofthesulfidedmolybdenumspeciesstabilizedonthealuminasupportisdiscussedbasedupontheanalysisoftheEXAFSdata.
简介:Thesynthesisandspectrophotometricpropertiesof2-(6-methyl-2-benzothiazolylazo)-5-diethylaminophenol(MBTAE),andtheuseofitasaprecolumnderivatizingreagenttoseparateCo(Ⅱ),Ni(Ⅱ),Rh(Ⅲ)andIr(Ⅳ)complexesbyHPLCarediscussed.Whenthemobilephaseconsistsofmethanol/water(90/10Ⅴ/Ⅴ),acetatebufferwithpH4.0and5×10-5mol/LEDTAsolution,thefourcomplexesCanbeseparatedwithin9minonODScolumn.Thedetectionlimits(20μLsamplesize)are0.059ppb,0.062ppb,0.053ppband0.049ppbforCo(Ⅱ),Rh(Ⅲ),Ni(Ⅱ)andlr(Ⅳ)respectivelyatasignal-to-noiseratioof3.
简介:Theoptimalconditionsforthecomplexationreactionofmeso-tetra(3-methoxy-4-hy-droxyphenyl)porphineT(3-M-4HP)Pwithplatinumandrhodiumarepresented.Beer’sLawisobeyedwhentheconcentrationofrhodiumisintherangeof0.45-1.15μg/25mL.Themolarabsorptivityofrhodiumwasfoundtobe1.99×106L·mol-1·cm-1at460nm.ThevalueofεPtwasfoundtobe6.28×105L·mol-1·cm-1bylinearregressionmethod.TheKcoefficientmethodandcompensatingcoefficientwereusedtodetermineplatinumandrhodiumsimultaneoulywithoutremovalormaskingoftheinterferentsinthesample.Theresultsforthedeterminationofplatinumandrhodiuminthemixedsolutionofplatinumandrhodiumaresatisfactory.