Ni-NH物种经C-N迁移形成C-N键的理论研究.docxVIP

Ni-NH物种经C-N迁移形成C-N键的理论研究

【摘要】目的：对Ni-NH物种经过C-N迁移形成C-N键的反应机理进行理论计算并对计算结果进行分析。对反应中Ni-NH物种中间体IM、迁移过渡态TS、酰胺化产物PC和Ni催化剂NiILn的几何结构、电荷与活化能进行计算。为进一步高效合成酰胺化产物提供理论参考。方法：运用密度泛函理论（DFT）的B3LYP泛函的计算方法。结果：计算得到Ni-NH物种中间体IM、迁移过渡态TS、酰胺化产物PC和Ni催化剂NiILn的几何结构、电子结构和能量，并绘制了反应势能面图。结论：由中间体IM→过渡态TS→PC+NiILn，C-Ni键长增长，C与N之间的距离缩短至1.470?，意味着C-Ni键断裂和C-N键的形成是同时进行的;计算的C-N键形成过程的活化能为11.7kcal/mol，意味着该步骤可以在实验条件下（室温）进行；计算的IM的能量比PC+NiILn高40.3kcal/mol，说明C-N形成步骤为放热反应；氮源上的N3原子电荷依次增加，金属Ni中心电荷减少，底物C原子电荷先增加后减少。

【关键词】形成C-N键；密度泛函理论；Ni-NH物种；反应机理；迁移

TheoreticalStudyonFormationofC-NBondbyC-NMigrationinNi-NHSpecies

[Abstract]Objective:ThepurposeistotheoreticallycalculateandanalyzethereactionmechanismofNi-NHspeciesundergoingC-NmigrationtoformaC-Nbond.Calculatethegeometricstructures,charges,andactivationenergiesoftheintermediatespeciesIM,migrationtransitionstateTS,amideproductPC,andNicatalystNiILninthereaction.Providetheoreticalreferencefortheefficientsynthesisofamideproducts.Method:Densityfunctionaltheory(DFT)usingtheB3LYPfunctionalforcalculations.Results:Thegeometricstructures,electronicstructures,andenergiesoftheintermediatespeciesIM,migrationtransitionstateTS,amideproductPC,andNicatalystNiILnwerecalculated,andthereactionpotentialenergysurfacewasplotted.Conclusion:TheformationprocessfromtheintermediatespeciesIMtothetransitionstateTStoPC+NiILninvolveselongationoftheC-NibondandshorteningofthedistancebetweenCandNto1.470?,indicatingsimultaneousbreakingoftheC-NibondandformationoftheC-Nbond.ThecalculatedactivationenergyfortheformationoftheC-Nbondis11.7kcal/mol,suggestingthatthisstepcanoccurunderexperimentalconditions(roomtemperature).TheenergyofIMis40.3kcal/molhigherthanthatofPC+NiILn,indicatinganexothermicreactionintheC-Nformationstep.Thenitrogenatomchargeonthenitrogensourceincreasessuccessi