The Electronic Spectra of Coordination Compounds配合物的电子光谱ppt课件.ppt

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1、TheElectronicSpectraofCoordinationCompoundsTheUV/Visspectraoftransitionmetalcomplexesshowsthetransitionsoftheelectrons.Analysisofthesespectracanbequitecomplex.ElectronSpectraTheUV/Visspectraareusedtodeterminethevalueof∆oforthecomplex.Thespectraarisefromelectronictransitionsbetweenthet2gande

2、gsetsofmolecularorbitals.Electron-electroninteractionscangreatlycomplicatethespectra.Onlyinthecaseofasingleelectronisinterpretationofthespectrumstraightforward.Obtaining∆oForad1configuration,onlyasinglepeakisseen.Itresultsfromtheelectronpromotionfromthet2gorbitalstotheegorbitals.The“toothed

3、”appearanceofthepeakisduetoaJahn-Tellerdistortionoftheexcitedstate.Theenergyofthepeak=∆o.GeneralObservationsd1,d4,d6andd9usuallyhave1absorption,thoughaside“hump”resultsfromJahn-Tellerdistortions.GeneralObservationsd2,d3,d7andd8usuallyhave3absorptions,oneisoftenobscuredbyachargetransferban

4、d.GeneralObservationsd5complexesconsistofveryweak,relativelysharptransitionswhicharespin-forbidden,andhaveaverylowintensity.QualitativeExplanationConsideraCr(III)complexsuchas[Cr(NH3)6]3+.Thegroundstateconfigurationis:________Atransitionfromthedz2dx2-y2dxytothedx2-y2,orthedyzordxztothedz2__

5、__________orbitalsinvolvearelativelydxydyzdxzminorchangeinenvironment.QualitativeExplanationThetransitionfromthedxzorbitalstothedz2orbitalsinvolvesarelativelyminorchangeintheelectronicenvironment.QualitativeExplanationConsideraCr(III)complexsuchas[Cr(NH3)6]3+.Thegroundstateconfigurationis:_

6、_______Atransitionfromthedz2dx2-y2dxytothedz2,orthedyzordxztothedx2-y2____________orbitalsinvolveamajordxydyzdxzchangeinenvironment.QualitativeExplanationThetransitionfromorbitalsinthexyplanetothedz2orbitalsinvolvesafairlymajorchangeintheelectronicenvironment.QualitativeExplanationSincethep

7、romotionofanelectronfromthet2gsetoforbitalstotheegsetcaninvolvedifferingchangesinenvironment,severalpeakswillbeseeninthespectrum.3dMulti-electronComplexesForcomplexeswithmorethanoneelectroninthe3d(and4s)orbitalsofthemetal,electroninteractionsmustbeconsid