Quantum Chemistry Studies on the Fe-Cu Interactions and 31p NMR in Fe（CO）3（Ph2Ppy）2（CuXn） （Xn = Cl2^2-, Cl-, Br-）.pdfVIP

27卷 11期 结 构 化 学(JIEGOUHUAXUE) Vo1．27， No．II 2oo8．11 Chinese j． Struct．Chem． 1339-1348 e QuantumChemistryStudiesonth Fe-CuInteractionsand31PNM R ln Fe(CO)3(Ph2Ppy)2(CuXn)(Xn=CI2，Cr，Br-)① xuXuan② LIQin．Yu FANGLiang SUN Shi—Lingb SUZhong—Min，b② (SchoolofChemistryandEnvironment,SouthChina NormalUniversity,Guangzhou510006,China) 。(InstituteofFunctionalMaterialChemistry,FaculytofChemistry, NortheastNormalUniversiyt,Changchun130024,China) ABSTRACT InordertostudytheFe-Cuinteractionsandtheireffectson PNMR，htestructures ofmononuclearcomplexFe(CO)3(Ph2Ppy)21andbinuclearcomplexesFe(CO)3(Ph2Ppy)2(CuXn)(2： Xn=C122-3：Xn=C1-，4：Xn=Br-)arecalculatedbydensityfunctionalhteory(DFr)PBE0mehtod． ， Forcomplexes1，3and4，hte PNMRchemicalshiftscalculatedbyPBE0-GIAO mehtodarein goodagreementwithexperimentalresults．The P chemicalshiftis82．10ppm inhtedesigned complex2．TheFe-Cuinteractions(includingFe_CuandFe Cuchragetransfer)mainlyexhibit theindirectinteractions．Moreover,hteFe-Cu(I)niteracfions(mostlyactingasaFe_p--~4SCuand aFe--C-*4Scuchargertansfer)incomplexes3and4raesrtongerhtanFe-Cu(II)interactions(mostly actingas F 4cuandcr-Fe__P 4cu)incomplex2．Incomplex2，htesrtongerFe Cuinterac- tions，actingas Fe-P一‘4cuchargetrna sfer,increasetheelectrondensityonPnucleus，whichcauses hteupfield31pchemicalshiftcomparedwiht mononuclearcomplex1 For3nad4，alhtoughalittle ． deshielding