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Paper
Dalton Trans., 2006, 3523 - 3527, DOI: 10.1039/b603285k
Spectroscopic and kinetic studies of the reaction of [CuI(6-PhTPA)]+ with O2
Michael P. Jensen, Emily L. Que, Xiaopeng Shan, Elena Rybak-Akimova, Lawrence Que and Jr.
Oxygenation of [CuI(6-PhTPA)](SbF6) in acetone at –90 °C produces a short-lived CuIII2(µ-O)2 intermediate that exhibits an oxygen-isotope-sensitive
Cu–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(µ-oxo)dicopper(III) intermediate in the former and a (µ-1,2-peroxo)dicopper(II) species in the latter.
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