Spectroscopic and kinetic studies of the reaction of [Cu I(6-PhTPA)]+ with O2

Michael P. Jensen, Emily L. Que, Xiaopeng Shan, Elena Rybak-Akimova, Lawrence Que

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Oxygenation of [CuI(6-PhTPA)](SbF6) in acetone at -90 °C produces a short-lived CuIII2(-O)2 intermediate that exhibits an oxygen-isotope-sensitive νCu-O mode at 599 cm-1 and an overtone at 1192 cm-1. The formation of this intermediate is very fast and is second-order in copper(i) complex, implying that two copper-containing species interact in the rate-limiting step or in pre-equilibrium steps prior to the rate determining step. The decay of this intermediate was facile even at -90 °C but did not afford any arene hydroxylation product. Interestingly, the effect of introducing a 6-phenyl substituent on the TPA ligand framework differs from that of a 6-methyl substituent, providing access to a bis(-oxo)dicopper(iii) intermediate in the former and a (-1,2-peroxo)dicopper(ii) species in the latter.

Original languageEnglish (US)
Pages (from-to)3523-3527
Number of pages5
JournalDalton Transactions
Issue number29
StatePublished - 2006


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