简介:Twonewdicyanamidecoordinationpolymers,{Mn(dmpz)[N(CN)2]2}2(1)and{Cu(dmpz)[N(CN)2]2}2(2)(dmpz=3,5-dimethylpyrazole),weresynthesizedandcharacterizedbysinglecrystalX-raydiffractionanalysisandIRspectroscopy.In1and2themetalionshavetwodifferentcoordinationmodes,whereoneiscoordinatedtofourdicyanamideanionsandtwomonodentatedmpzmoleculestoformaslightlydistortedoctahedralgeometry,whiletheotheradoptsoctahedralgeometry,surroundedbyfournitrileNatomsandtwoamideNatomsofthedicyanamideanions.Bothcomplexescontaintwoalternatingchainsthatareparalleltoeachother.
简介:Startedfrom5-hydroxy-2-pentanone,(R)(E)-3,7-dimethyl-2-octene-1,8-dioicacid,callosobruchusicacid,wassynthesizedviafivestepswithD-(-)-camphorsultamasthechiralauxiliary.Itwasofgoodopticalpurityandyield.
简介:Tetrabutylammoniumorpotassiumsaltsoforganometalllicderivativesoflacunarypolyanion(RM)3P2W15O59^n-(RM=CpTi,CpZr,C4H7O2SnorC5H9O2Sn)havebeenpreparedandstructurallycharacterizedbyelementalanalysis,IR,UV-Vis,^1HNMRand^183WNMRspectroscopies.Thetitlecomplexesexhibitantitumoractivityinvitro.
简介:Four1,2,3-trisubstitutedimidazoliniumiodideswhichwereusedas5,10-+CPh-THFmodel(7-10)atformicacidoxidationlevelweresynthesized.Thebenzylidynegroup(phenyl-substitutedonecarbonunit)transferreactionsfromthesecompoundstoGrignardreagentwerein-vestigated,andthereactionsofthesecompoundswithKBH4andNaOHwerealsostudied.
简介:8,8′-Dibromo-6,6′,7,7′-tetramethoxy-5,5′-diisopropyl-3,3′-oxydimethylenedinaphtho[2,1-b:2′,1′-d]furan,C32H30Br2O;M.W.=670;triclinic;spacegroupP1;a=8.896(2),b=10.216(1),c=10.423(1)A,α=108.48(1),β=119.36(1),γ=99.26(1);V=723.5A3;Z=1,Dcal.=1.479g.cm-3.MoKα=28.11cm-1,F(000)=326,T=293K.Thestructurewassolvedbydirectmethodandfull-matrixleast-squaresrefinementconvergedatR=0.034for2377observedreflections.Theoxygenatominseven-memberedringexistsinadisorderedarrangement.Bothbisnaphthaleneandoxygen-containingfive-memberedringhaveplanarconformationswithdihedralangle6°,showingmarkedaromaticfeature.
简介: Enantioimericallypure1,l'-bi-2-naphthol(BINOL)1anditsderivativesareimportantchiralligandsandauxiliariesforanumberofasymmetrictransformations1suchasaldolcondensations,alkylations,Diels-Alderreactions,Michaeladditions,epoxidations,etc.Opticallypure1andtheirderivativeshavealsobeenusedextensivelyinchiralrecognition,chiralseparationandintheconstructionoffunctionalisedmaterials2.Furthermore,(R)-and(S)-BINOLarealsofundamentalstartingmaterialsforthesynthesisofalargevarietyofotherchiralbinaphthylssuchasMOP(2c),NOBIN(2d)andBINAP(2e).Asaresultthedevelopmentofefficientandeconomicmethodsforthepreparationofopticallypure1hasattractedmuchattentioninrecentyears3andnovelmethodsfortheresolutionof(±)-1continuetobedeveloped.……
简介:The2-Dheteronuclearcoordinationpolymer{[Ag4Fe2(SCN)12(H2O)2][(inaH)2(H2O)2]}n(1)(inaHistheabbreviationofprotonatedisonicotinicacid)withchemicalformulaC24H20Ag4Fe2N14O8S12hasbeensynthesizedandcharacterizedbysinglecrystalX-raydiffraction,elementalanalysisandIRspectroscopy.TheAgES2ringsconnecttwokindsofoctahedralgeometriesofFe(Ⅲ)ions,[Fe(NCS)6]^3-and[Fe(H2O)E(NCS)4]^-unitswithbridgingthiocyanateionsleadingto2-D[Ag4Fe2(SCN)12(H2O)2]^2-anionframework.Fourkindsofringsincludingtheunprecedentedthirty-twomemberedAg4Fe4(SCN)8ringssharecomersoredgesinthe2-Danionlayerstructure.AllthiocyanatescoordinatetothemetalionsaccordingtotheHSABprinciplewithNatomsbindingtotheFe(Ⅲ)ionsandwithSatomsbindingtoAg(I)ions.Pronoatedinacationsstabilizethelayerstructureascounterionsandhydrogenbondswereformedwithinthepronoatedinacationsdimerandbetweenthedimersandthelatticewaters.Crystaldata:Mr=1560.44,triclinic,P-↑1,a=0.76082(1)nm,b=0.9234nm,c=1.85611(4)nm,α=103.0170(10)°,β=93.7780(10)°,γ=97.4080(10)°,V=1.25385(3)nm^3,Z=1,μ(MoKα)=2.650mm^-1,Dc=2.067g·cm^-3,F(000)=758,R1=0.0412,wR2=0.1003.
简介:SodiumdithioniteinitiatedsulfinatodehalogenationofBrCF2CF2Risstudied.
简介:Thecanonicalandlocatizedmolecutarorbitersof[NCCuS2NoS2]2-clusterwerecalculatedbymeansofCNDOquantumchemistrymethod.Thentheenergyandpropertiesofcorrespondingchemicatbondswerediscussed,especially,Cu-Sb-NothreecenterconjugatedπbondsandNo-St-Noconjugatedπbondswereaccountedfor.
简介:NOVELOXIDATIONOFHEXABENZYLHEXAAZA-ISOWURTZITANEBYMe2CHNO2/CuCl/Py/O2XiaoPeiGUAN;HongYAN;JianGuangSUN;YongZhongYU(ScholofChe?..
简介:STUDIESONGLYCOSIDESXVII─STEREOSELECTIVESYNTHESISOF(2,6-DIMETIIOXY-4-ETHOXYCARBONYL)PHENYL6-O-ACETYL-2,3,4-O-BENZYL-β-D-GLUCOP...
简介:Thecombinationofboth4,4′-bipyridine(4,4′-bipy)anddihydrogenphosphateanionligandswithcopper(Ⅱ)resultsintheformationofanovellayeredcompoundCu(4,4′-bipy)2(H2PO4)2(H2O)2.ThecrystalstructurecomprisesdiscreteneutralCu(4,4′-bipy)2(H2PO4)2(H2O)2units.Thecopperatom,locatedonthecrystallographictwofoldaxis,iscoordinatedwithtwonitrogenatomsofterminal4,4′-bipyligandsandtwowatermoleculesattheequatorialpositions,andtwodihydrogenphosphateoxygenatomsattheaxialpositions,forminganelongatedoctahedron.Thecomplexisatwo-dimensionaldistortedrhomboidalnetworkpossessingtwokindsofrhomboidswithdimensionsofca.1.6792nm×0.3203nmand1.2778nm×0.3198nm,respectively.Thetwo-dimensionalnetworksarestackedparallellyoneachotheralongc-axistogiveanextendedthree-dimensionalchannelnetworkwithaninterlayerdistanceofca.0.5030nm.Crystaldata:triclinic,spacegroupP-1,a=1.0253(2)nm,b=1.4501(3)nm,c=0.79715(16)nm,α=97.91(3)°,β=90.99(3)°,γ=85.54(3)°,V=1.1703(4)nm3,Z=2,R=0.0892,wR=0.2451.
简介:Copolymerizationofstyrene(St)andisoprene(IP)wascarriedoutwithacatalystsystemcomposeaofanhydrouslanthanidechloridehexamethylphosphoramidecomplex(LnCl3·HMPA)andaluminumorganiccompound(AOC).Amongthecatalystsexamined,catalystNdCl3·HMPA/AI(i-Bu)3showedahighactivityinthecopolymerizationundercertainconditionsgivingcopolymers(5%—15%Stcontent)withhighcis-1,4microstructureinIPunits(>95%).TheeffectsofHMPA/Ndmolarratio,Al/Ndmolarratio,monomer/Ndmolarratio,Stfeedratio,andthereactiontimeoncopolymerizationwereexaminedwiththiscatalyticsystem.Theobtainedcopolymerswerecharacterizedby^1Hand^13CNMRspectroscopiesandgel-permeationchromatography(GPC).
简介:Thethermalbehavior,mechanismandkineticparametersoftheexothermicfirst-stagedecompositionofthetitlecompoundinatemperature-programmedmodewereinvestigatedbymeansofDSC,TG-DTGandIR.Thereactionmechanismwasproposed.Thekineticmodelfunctionindifferentialform,apparentactivationenergy(Ea)andpre-exponentialfactor(A)ofthisreactionare(3/2)(1-a)[-In(1-a)]^1/3,185.52kJ/moland10^17.78s^-1,respectively.Thecriticaltemperatureofthethermalexplosionofthecompoundis201.30℃.Thevaluesof△S^≠,△H^≠and△G^≠ofthisreactionare72.46J/(mol·K),175.1kJ/moland141.50kJ/mol,respectively.
简介:Anewapproachtothesynthesisof2,2″-biflavanonesbythereductivedimerizationoffla-vonesisreported.Theproducts,theracemateandmesobiflavanones,havebeenseparatedandtheirstructureshavebeendeterminedonthebasisoftheirspectraldata.Theconfigurationof3bhasbeendeterminedbyX-raycrystallographyaswell.
简介:Theopen-frameworkironphosphateFe2^111Fe1.5^11(PO4)3washydrothermallysynthesizedandcharacterizedbyelementalanalysis,IR,EPR,XPSandsinglecrystalX-raydiffractionanalysis.Thetitlecompoundcrystallizedinthetriclinic,spacegroupP-↑1witha=0.64724(4)nm,b=0.79651(6)nm,c=0.94229(5)nm,α=104.447(2)°,β=108.919(4)°,γ=101.741(4)°,V=0.42302(5)nm^3,Z=1andR1(wR2)=0.0307(0.0793).CrystaldatawerecollectedonaRigakuR-AXISRAPIDIPdiffractometerwithMoKα(λ=0.071073nm)at293(2)Kintherangeof2.43°
简介:采用直接动力学的方法,对多通道反应体系Br+CH3S(O)CH3进行了理论研究.在BH&H-LYP/6-311G(2d,2p)水平下获得了优化几何构型、频率及最小能量路径(MEP),能量信息的进一步确认在MC-QCISD(单点)水平下完成.利用正则变分过渡态理论,结合小曲率隧道效应校正(CVT/SCT)方法计算了该反应的两个可行的反应通道在200K~2000K温度范围内的速率常数.在整个反应区间内,生成HBr的反应通道与生成CHa的反应通道存在着竞争,前者是主反应通道,后者是次反应通道.变分效应和小曲率隧道效应对反应速率常数的计算影响都很小.理论计算得到的两个反应通道的反应速率常数与实验值符合得很好.