Abstract
The reactivity of σ-yne-ols complexes has been studied in the case of tertiary benzylic alcohols. Isomerization into new cyclised η 1-1,5-dihydrofuran complexes has been observed with molybdenum compounds. When protonated at low temperature, the iron compounds yield isolable but thermally unstable cationic complexes. Strong evidences for a π-cumulene structure of these complexes are given from their reactions with nucleophiles: methoxide ion yields different products by alkoxycarbonylation reactions at the C(2) or C(3) carbon atom of the coordinated cumulene while amines readily add to the C(4) terminal carbon atom.
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