Abstract
(Cyclobutenyl)carbene tungsten complexes are shown to rearrange to 1-tungsta-1,3,5-hexatrienes. Azabicyclo[4.2.0]octadiene (bis)carbene tungsten complexes 3a−c, which served as model compounds in these studies, were generated by [4 + 2]- and [2 + 2] domino cycloaddition of 2 equiv of (1-alkynyl)carbene complex (CO)5WC(OEt)C⋮CPh (1) to alkenyl imidates RCHCHC(OEt)NR1 (2a−c) (R = Ph, Me; R1 = Me, i-Pr). Compounds 3 are stable in the solid state at 20 °C but rearrange in solution to 1-metalla-1,3,5-hexatrienes 7a−c by ring opening of the cyclobutene ring and subsequent 1,3 hydrogen migration. Compounds 3a and 7b were characterized by crystal structure analyses.
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