Abstract
A study has been made of the reactivity of the σ(Pd-Csp2) bond in the di-μ-chloro-bridged cyclopalladated complexes [Pd{(η5-C5H3CHNC6H4C6H5-2)Fe(η5-C5H5)}(μ-Cl)]21a and [Pd{(C6H4-2-C6H4)NCH(η5-C5H4)Fe(η5-C5H5)}(μ-Cl)]21b {which differ in the nature of the metallated carbon atom Csp2, ferrocene or Csp2, biphenyl, respectively} towards the alkynes, R1CCR2 {with R1 = R2 = Et; R1 = H, Me or Ph, and R2 = Ph; or R1 = R2 = CO2Me}. Thus palladacycles containing seven-, eight-, nine- and ten-membered rings have been isolated and characterized. The crystal structure of [Pd{(EtCCEt)2(C6H4-2-C6H4)NCH(η5-C5H4)Fe(η5-C5H5)}Cl] has also been determined and confirms the presence of a [6, 6, 10] tricyclic system arising from fusion of the two hexagonal rings of the biphenyl group and a ten-membered palladacycle generated through bis(insertion) of hex-3-yne into the σ(Pd–Csp2, biphenyl) bond in 1b.
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