auⅲschiffbase配合物催化剂在羰化反应中的催化性能研究word格式论文.docx

reactionwere14.7%,92.5%,andnoAu(0)generatedunderthereactionconditions:120℃,Pco/PO2=2:1,P总=3.0MPa,t=4h,indicatingthattheSchiffbaseandCuCl2couldstabilizedAu(III)inCOatmosphere.Afterthecatalystreusedfor6times,theiractivitykeepalmostunchanged.Inthecontinutionofthenewcatalystsystemintheoxidationcarbonylation,anewtypehomogeneouscatalyticsystemwasdeveloped,Au(III)/Schiffbase/halide,whichshowedgoodactivityinmethanoloxidativecarbonylationwasfound.The Schiff baseligand,reactiontemperature,pressure,amountandtypeofhalideadditivesonthecatalyticperformance was studied in detail. At an optimized condition: 120℃, Pco/Po2==2:1,Ptotal=3.0MPa,3h,Metnaol/Au(III)=5060(mol/mol),KI/Au(III)=4,onthe[AuCl2(phen)]Cl/KI,theconversionofmethanolwas10.8%,theselectivitytoDMCwas98%andtheTOFwas138.9h-1.TheactivityofthisnewcatalyticsystemincreasedsubstantiallycomparingwithconventionalCucomplexcatalyst.Toextendthepracticalapplicationofgoldinhomogeneouscatalysis,theexperimentalstudypresentedhereindescribesahomogeneousgold-catalyzedcarbonylationofalkylnitritetodialkylcarbonate.Theligandtype,amountofhalideadditiveswerestudiedindetail. The catalytic esults shows that under 80℃, Pco=3.0MPa, 5h, KI/Au(III) =4(mol/mol),[AuCl2(phen)]Cl/KIexhibitedthebestperformancewiththeconversionofethylnitrite78.2%,theselectivityofDEC91.7%.Thiscatalyticsystemisalsocapabletoapplytolow-carbonalkylnitrite,whichsuggestsgoodselectivityintheproductionofcorresponding carbonate. NoAu0generatedinthiscatalyticsystem. Both the ligandandpromoterplaycrucial roles inincreasingthecatalyticactivityofthegoldioninahomogeneousreaction.Au(III)/Shiff-base/CuCl2wasthenemployedasacatalystinthecarbonylationofethylnitrite,underthesamereactionconditions,on[AuCl2(phen)]Cl/KI/CuCl2,theconversionandtheselectivity wereenhancedupto80.6%and99%,andthecatalystcouldbeusedforseveraltimes.Basedon theexperimentalresults ofUV-vis,ESI-MSandcyclicvoltammetry, theoxidationstateofgoldduringthereactionandtheroleofKIwerediscussed.[AuI2(phen)]+wasconsideredasaninter