4-Chloroaniline and its N,N-dimethyl derivative are photostable in cyclohexane but undergo efficient photoheterolysis in polar media via the triplet state and give the corresponding triplet phenyl cations. CASSCF and UB3LYP calculations show that the 4-aminophenyl triplet cation has a planar geometry and is stabilized by >10 kcal mol-1 with respect to the slightly bent singlet. The triplet has a mixed carbene-diradical character at the divalent carbon. This species either adds to the starting substrate forming 5-chloro-2,4¢-diaminodiphenyls

Generation and reactivity of the 4-aminophenylcation by photolysis of 4-chloroaniline

MELLA, MARIELLA;FAGNONI, MAURIZIO;FRECCERO, MAURO;
2001

Abstract

4-Chloroaniline and its N,N-dimethyl derivative are photostable in cyclohexane but undergo efficient photoheterolysis in polar media via the triplet state and give the corresponding triplet phenyl cations. CASSCF and UB3LYP calculations show that the 4-aminophenyl triplet cation has a planar geometry and is stabilized by >10 kcal mol-1 with respect to the slightly bent singlet. The triplet has a mixed carbene-diradical character at the divalent carbon. This species either adds to the starting substrate forming 5-chloro-2,4¢-diaminodiphenyls
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11571/108060
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