REACTION OF DIOXYGEN WITH A CROSS-CONJUGATED CARBON-CARBON DOUBLE BOND IN A BIS-MACROCYCLE DIIRON COMPOUND

摘要

Dioxygen at atmospheric pressure attacks a cross-conjugated carbon-carbon double bond in a diiron complex to form two, like, keto macrocyclic iron(II) complexes. This reaction occurs with high yield in both solution and in the solid state. A dioxetane intermediate is, therefore, invoked. The rate of the reaction is very dependent on the nature of the axial ligands on the low-spin iron(II) ions in the bimetallic complex. The rate is at least a factor of 10(4) faster with DMF ligands than with CH3CN axial ligands. This rate dependence is explained by stabilization of a peroxo biradical transition state en route to a dioxetane intermediate. The keto-macrocyle product has the carbonyl group conjugated with a beta-diimine in a six-membered chelate ring. The conformation of this keto macrocycle is fixed on the NMR time scale and the spectra of all ten non-equivalent protons in the complex can be unambiguously assigned. The keto beta-diimine ligand is an excellent pi-acceptor as indicated by the high Fe(II) to Fe(III) oxidation potential of the compound and by the Mossbauer spectrum, which shows a low value for the center shift and a high value for the quadrupole splitting parameter. (C) 1997 Elsevier Science S.A. [References: 9]