Reactions of coordinated cyclic polyolefins. The mechanism of the pericyclic [4,4]-sigmahaptotropic rearrangement; a kinetic study. Crystal structure of tricarbonyl[(2,3,4,5-η)bicyclo[4.2.1]nona-2,4-diene-7,7,8,8-tetracarbonitrile]iron

Abstract

The novel [4,4]-sigmahaptotropic rearrangement II → IV, in which a σ-bonded group and a Fe(CO) 3 unit exchange bonding sites antarafacially across a four carbon skeleton, has been shown by kinetic data to involve a concerted, non-synchronous, one step process. First order rate constants for the rearrangement at 23°C are k 1.25 × 10 −6 s −1 (acetone) and k 2.2 × 10 −5 s −1 (methanol), with activation parameters Δ H # 21 kcal mol −1 and Δ S # −15 e.u. (acetone). The moderate value of the ratio of k in methanol to that in acetone, viz. 18, indicates that although a minor charge separation develops upon activation, no intermediate is formed. The least motion pathway mechanism is shown to involve a Berry pseudorotation about the metal, which maintains the bonding interaction between the metal and the organic fragment orbitals during the rearrangement. Topologically this rearrangement corresponds to a [σ2 a + (σ2 s + π2 a)] thermally allowed pericyclic reaction. The structure of the rearranged complex IV was determined by single-crystal X-ray diffraction.