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| - Equilibrium between η2-(o-Ethynylbenzoyl)rheniumComplexes and Rhenium Isobenzofuryl CarbeneComplexes and Subsequent Reactions of IsobenzofurylCarbene Complexes
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| - The η2-(o-ethynylbenzoyl)-Re complex 2 rearranged at room temperature to the isobenzofuryl-Re carbene complex 3 in an equilibrium process. Isobenzofuryl carbene complex 3 reacted with dioxygen to give the Re η2-ketone complex 5; 17O-labeling showed unexpected regiochemistry.
- Thermal rearrangements of η2-(o-ethynylbenzoyl)-Re complexes 2 produced isobenzofuryl-Re carbene complexes 3. This reaction might proceed via nucleophilic attack of the carbonyloxygen on the Re-bound alkyne or might proceed through a [1.5,1] Re shift followed by anelectrocyclic ring closure. The two species, alkyne complex 2 and carbene complex 3, wereobserved at equilibrium. Isobenzofuryl carbene complexes 3 were characterized by 1H and13C NMR spectroscopy and by trapping via Diels−Alder reactions with DMAD. Air oxidationof the equilibrium mixtures of 2 and 3 led to oxidation of the isobenzofuryl carbene complexes3 to unexpected Re η2-ketone complexes 5. Studies with 17O-labeled dioxygen are consistentwith oxygen addition to the isobenzofuran followed by rearrangement of the resultingendoperoxide that involves movement of the furan oxygen to the η2-ketone site in 5.
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