C-N vs. C-C Bond Photodissociation in N-(tert-butyldiphenylmethyl)aniline英文文献资料.docVIP

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C-N vs. C-C Bond Photodissociation in N-(tert-butyldiphenylmethyl)aniline英文文献资料.doc

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C-N vs. C-C Bond Photodissociation in N-(tert-butyldiphenylmethyl)aniline英文文献资料

Vol.06 INTERNATIONAL JOURNAL OFPHOTOENERGY 2004 C-Nvs.C-CBondPhotodissociation in N-(tert-butyldiphenylmethyl)aniline StylianosGaras,MichaelG.Siskos,andAntoniosK.Zarkadis? Department ofChemistry, University ofIoannina, 451 10Ioannina, Greece Abstract. Thedirectphotolysis ofthetitleanilinecompound Ph2(Me3C)C-NHPhinacetonitrile with248nm laser light results in the dissociation of the C-N bond giving the corresponding (tert-Bu)diphenylmethyl radical 1a? and the anilino radical PhNH? detectable by ns-laser ?ash photolysis (LFP) and ESR spec- troscopy. The same radical 1a? is also produced from the corresponding (tert-Bu)diphenylmethyl chloride Ph2(Me3C)C-Cl either photolytically in MeCN through C-Cl bond homolysis or pulse radiolytically in THF; the (tert-Bu)diphenylmethyl cation is also detected, however, at sorter time scales because of its high reac- tivity in the solvent MeCN. At higher laser pulse intensities the radical 1a? isreexcited by asecond photon leading through electrocyclization to the 4a,4b-dihydro-9-tert-butyl?uorenyl radical (DHBF?) and ?nally to ?uorenyl products. Product analyses ofsteady statephotolyses using GCandGC-MS gaveasprincipal prod- ucts(tert-Bu)diphenylmethane, aniline andvarious 9-substituted ?uorenyl derivatives, corroborating further theprimary C-Nbond cleavage andtheformation oftheradicals 1a? andPhNH?.Other conceivable dissoci- ation pathways leading tothe C-CMe3 orN-H bond rupture were not observed. 1. INTRODUCTION The photodissociation of the benzylic bond C-X (X=Hal, +OH2, OCOR, OR, +SR2, ?PO3H, +NR3, CR3 NH CMe3 1 NH etc.) of molecules in solution continues to be the fo- cus of extensive product and time-resolved spectro- scopic [1] as well as of theoretical studies [2]. The reason lies not only in the fundamental problem of the competition between homolytic and heterolytic C- X splitting [1b,3], but also in the many-sided conse- quencesinappliedphotochemistry (photochromic ma- terials,photodeprotection techniqu