Abstract
Two homologous complexes of the type [(NHC)AuI–Ar], in which the aryl substituent was either phenyl or pentafluorophenyl, were prepared. Treatment of [(IPr)AuIC6F5] with PhICl2 leads directly to the expected AuIII oxidation addition product [(IPr)AuIII(Cl)2C6F5]. This complex is thermally stable but undergoes photochemical reductive elimination to deliver [(IPr)AuICl] and C6F5Cl. In contrast, the reaction of [(IPr)AuIPh] with PhICl2 does not deliver an isolable AuIII oxidation addition product but rather leads directly to the formation of [(IPr)AuICl] and PhCl, presumably via a [(IPr)AuIII(Cl)2Ph] intermediate. These related reactivity pathways are rationalized on the basis of the electronic structures of the two [(NHC)AuI–Ar] complexes.
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