【word】 C-H键核自旋偶合常数和伸缩频率的最大键级杂化轨道研究

【word】 C-H键核自旋偶合常数和伸缩频率的最大键级杂化轨道研究 C-H键核自旋偶合常数和伸缩频率的最大 键级杂化轨道研究 2010??8?) ?B16???B3?d ?????)?1????????(???K??????) JournalofAnqingTeachersCollege(NaturalScienceEdition) Aug?a2010 VOI?a16No?a3 CVgH?R?9???????)?9?????9?5?????????7?R???j?e?????g?? ?????o1?r???e??2 (1?a?????)?1?????e???e???????r???????)???????2???????????r????????246011?r 2?a?????)?1?7???e???a?????????????r????????241000) ???n?C?5?-PM3???]?o?????7?????????7?3?????????????7?R???j?e?????????r?????????c???I?e?)?????j?e ?????r???)????????CVgH?R?9???????)?9?????9?5???????????????l?a?g?????8?????I?e?)???m?n?r????H?R?9?? ?????)?9?????9?5?????a???????a?r???I?e?)???m??cVgH?9???????)?9?????9?5?????L?????????????????????j?e ???-?r?Q?????????R?3????????????????1JcH????H?????????????????? ???????a ???R???C???)?9???N?9?5?????N???7?????????7?3???????N???7?R???j?e???? ?m?)?3?????C0641???R?(???2?CA?????5???C1007Vg4260(2010)03--0085--04 0?T?? ?9???????)?9?????9?5?????????????g???3??????????F2?????????f?R???????????-???????J?? ???l??F0?????7???J???????9???????)?9?????9?5???????3??????????????[1--10]F0?????????????? ???????g???????D?????e?????y?J???D???r?U?????F?????????????)?9?????9?5?????????5?-?7????F2 ?????]???w??????????????[1??F0?????]?7????F2?????]???????????n?F???????????r?g?????-???7?3 ????????F0????????????F2?????????????????????????y?????????J????????F0?B?????-PM3???]?o ?????7?????????7?3??????????VhVS3?????7?R???j?e????(MBOHO)????m3?????r?f?????9???????)?9 ?????9?5?????a???????j?e????s?f???????????a?????r???F1?a?rcH??IJCH?????????????l?r?????????n ?r?e???????u??CVgH?R???)?9?????9?5???????????DF0 1???B?????l Mtiller??Pritchard[143???????????R???????????9???????)?9???a?R???7?-?r???]?y?a?f?R???? ?j?e???????S???r?????????)?9???L??????Ramsey?p??????Fermi?????????????r???)?9??J???a?? ?????????j?e????5?f???f?????r?????????????R????????AVgB?r?????)?9???a??AB?a?j?e??????5?f?? ???J?????????????l(MP??)?C 1JAB????(s?6)A(s?6)B+b(1) ?l?ma??b?Q?????N(s?6)AF2(5?6)F0?3?]?Q???)????AF2B???????j?e??????5?f??F0 ?+??H?????-?f?R???r(s?6)H=100?r?s????CVgH???)?9?????r???u(1)???????????e?r?????l?Q?C 1JcH=a(5?6)c+b(2) ?l?m(s?6)F0?y???????-?????fCVgH?R???j?e??????5?f?????3???ra??b?Q???????????)????F0 Brown[103??Rock[1s3?????3?]??????CHF0??R???3???mCVgH?9?5???9??(KcH)?a1JcH???????a ?????7?????l?C ??H(KcH)=?C1JcH+Z(3) ???K?x???d?C ?????????C ???6?????C 2009Vg11Vg12 ???????O?2?????K?????????g??????(KJ2008A12zc)?r???????O?2???h?????????????????? (2010SQRLl08ZD)?Y??F0 ?????o?r?Z?r???????????a?????)?1?????e???e?????????????r?????r?L???????????e???????????)???g??F0 86???????)?1????????(???K??????)2010?? ?l?mk??z?Q???????????)?????r?3(2)?l????(3)?l???????F?????+CVgH?R???????????????j?e???? ?f??????CVgH?9?5?????????u???D?????l?C vcH=K(s?6)c+L(4) ?l?mK??L?r?Z?y???????)??????F0 2?????????a???? ???-PM3???]?o?????7?????????7?3???????????????c???I?e?)???????????h?e?r?????????8?3 ???????k?????????k?r???5?-MBOHO???????3???m?8???????j?e?????r???F?8???????j?e??????s?f ??F0???????F???????j?e??????s?f???3?]?c????1?mF0 ??1CVgH?Rs?????f??F2?9???????)?9?????9?5???? 3?d?????o?r???e???CCVgH?R?9???????)?9?????9?5?????????7?R???j?e?????g????87?? ???C?M??(s)??(a)?3?]???QCVgH?R?-?3???????????????????eF0 ?5?-?(?????????lb--?????r?3??1?m???????F??C?????j?e????S?f???????D?3?]????????1JcH?? ???DEVt61??1,??C?l4?????D??61???????7???)?r?+???e?u??(FORTRAN????)???)???F????CVgH?R?9???? ???)?9?????9?5???????????????l?3?]?Q?C 1JcH=5?a07862(s?6)c??4?a16892(5) VCH=17?a01479(s?6)c+2514?a59209(6) (5)?l??(6)?l???????????3?]?Q0?a95347??0?a97844?r?(???????3?]?Q10?a90761Hz?? 28?a14347cm??F0 Exp?aF0VhVg2 ??1CVgH?R?9???????)?9???????D???????D??????????2CVgH?R?9?5?????????D???????D???????? ?3??1?m???????8?3?????j?e??????S?f???3?]????(5)?l??(6)?????r???F???8?????I?e?)???? ???)?9??1JF0H???9?5????vcH?3???????D???3?]?c????1?m?r?????????D???????D?????????3???r???? 1F0?+??1?p?c?????????u???r?9???????)?9?????9?5???????3???????????a?????D?y?W?3??????F0?? ?4?6????????(??1??2)?3???????r?8???????????l?r???7?????7?????r?????????3?]?Q0?a95347F2 0?a97844?r?(???????3?]?Q10?a39972Hz?r27?a53730cm???r?L???o??? r???????-?W???1?????N???????? ???????????r???3???m?????????LF2?????0??????C???????j?e?????????V???????e???????n?r?? 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[1]PopleJAF0MclverJWF0OstlundNS?aFiniteperturbationtheoryfornuclearspincouplingconstants[J]?aChemPhysLett?r1967?rl (1)?C465--466?a [2]FukuiH?rTsujiT?rMuiraK?aCalculationofthenuclearspinVgspincouplingconstants?a3?asigma?a??and?api?a--Electroncontributions insomesimpleunsaturatedhydrocarbons[J]?aJAmChemSoc?r1981?r103(3)l3652Vg3653?a [3]SekinoH?rBartlettRJ?aNuclearspin--spincouplingconstantsevaluatedusingmanybodymethods[???aJChemPhys?r1986?r85(7)l 3945Vg3949?a [4]HuZM?rZhanCG?aMaximumbondorderhybridorbitals?aO??aCorrelativitywithC--HandcVgCspinVgcouplingconstants[J]?a TheorChimActa?r1993?r84(6)?C521Vg533?a [5]ZhanCG?rYeSYF0ZhuWX?reta1?aAstudyofthecorrelativitybetweentheabinitiomaximumbondorderhybridorbitalcalculation resultsandthenuclearspin--spincouplingconstants[J]?aJMolStruct(THEOCHEM)?r1995?r337(1)?C67Vg76?a [6]?(???r???r???a?????R??????????NMR???)?9???????K?j?e?????g??[J]?a?O?+???j???r1998?r15(I)?C45Vg54?a [7]???9???r?(???r???r???a?????R??VSc-1H???9???????)?9?????3???g??[J]?a???+???j???r2003?r20(3)?C225--229?a Vh [8]Kamiefiska--TrelaK?aCorrelationofthe13C--13CspinVgspincouplingconstantswiththestretchingforceconstantsofsingleand doublecarbon--carbonbonds[J]?aSpectrochimcaActa?r1980?r36(3)1239 --244?a [9]Kamiefiska--TrelaK?aCorrelationoftheVSC--13cspin--spincouplingconstantswiththestretchingforceconstantsoftriplecarbon --carbonbonds[J]?aJMolStructF01982?a78(1--2)?C121Vg128?a [10]BrownTL?rPuckettJC?rCorrelationoftheC-Hstretchingforceconstantwiththenuclear13cVgHcouplingconstantC]]?aJChem Phys?r1966?r44(6)l2238Vg2242?a [11]CarmichaelI?aAbinitioquadraticconfigurationinteractioncalculationofindirectNMRspin??spincouplingconstants[J]?aJPhys Chem?r1993?r97(9)?Cl789Vg1792?a [12]?????o?r???n?a???e???aPM3???]?o?????7?????????7?3??????[J]?a?????)?1?????????C???K???????r2007?r13(2)?C49Vg52?a [13]Zhan?rCG?rHuZM?aMaximumbondhybridorbitals[J]?aTheorChimActa?a1993F084(6)?C511--520?a [14]MlillerN?rPriehardDE?aVSCsplittingsin protonmagneticresonancespectra?aIHydrocarbons[J]?aJChemPhys?r1959(31)l768Vg 771?a [15]RockSL?rHammakerRM?rCorrelationoftheC--Hstretchingfrequencyand13cVgHcouplingconstantforsubstitutedaldehydes [J]?aSpectrochimActsPartA?r1971?r27(9)?C1899Vg1907?a [16]MckeanDC?aIndividualCVgHbondstrengthsin simpleorganiccompounds?Ceffectsofconformationandsubstitution??]?aChemSoc RevF01978?r7(3)?C398Vg422?a MaximumBondOrderHybridOrbitalStudyof theCVgHCouplingConstantsandStretchingFrequenciesofHydrocarbons HUANGRong-yil?aYEShi-yon92 (1?aAnhuiKeyLaboratory ofFunctionalCoordinationCompounds?rSchoolofChemistryandChemicalEngineering?r AnqingTeachersCollege?rAnqing246011?rChina?N2?aCollegeofChemistryandMaterialScience?r AnhuiNormalUniversityF0Wuhu241000F0China) Abstract?CAsimplerelationshipbetweenthenuclearspinVgspincouplingconstantsandthestretchingfrequencies of theC??Handthes--characterofhybridorbitalsisformulated?aTherelationshipobtainedisappliedtothecalculationof the 1 JcHand??Hforanumberofhydrocarbonsbasedonthemaximumoverlapsymmetrymolecularorhital(MOSMO) methodunderPM3approximationandthemaximumbondorderhybridorbita l(MBOHO)procedure?aThecalculatedvalVg uesarewellingoodagreementwiththe experimentaldata?rwhichsupportsthes--characterofthe corresponding Catom inhydrocarbonsisdominantfactorsindeterminingcarbon--HydrogenspinV gspinCouplingconstantsacrossonebondand theC??Hstretchingfrequencies?aThus weareabletointerpretandcalculatethe 1 JellandvcHvaluesbasedonthesimple valencebondtheory?a Keywords?Ccouplingconstant?rstretchingfrequency?rmaximumoverlap symmetrymolecularorbital,aximumbondorVs derhybridorbital