Abstract
The cycloaddition of 1-phosphabutadienes with AuI and PdII proceeds very differently when the hydrogen substituent in the 3-position is replaced by methyl. Specifically, 1-phosphaisoprene [Mes*P═C(Me)─CH═CH2, E-1a] was treated with [Au(tht)Cl] (tht = tetrahydrothiophene) to afford a phosphaalkene-substituted phosphacyclohexene binuclear AuCl complex. This intermolecular [4 + 2] cycloaddition is analogous to the Diels–Alder reaction and proceeds via the end-on complex [Au(E-1a)Cl], which was also isolated. In contrast, the reaction of 1-phosphabutadiene Mes*P═C(Me)─C(Me)═CH2 (E-1b) with [Au(tht)Cl] selectively afforded the 1-phosphet-2-ene-AuI complex [CH2─C(Me)═C(Me)─P(Mes*)AuCl] in near quantitative conversion. This intramolecular [2 + 2] cycloaddition also occurred when E-1b was reacted with [Pd(η3-C3H5)(μ-Cl)]2 or [Pd(cod)Cl2] (COD = cyclooctadiene) to afford complexes [CH2─C(Me)═C(Me)─P(Mes*)Pd(η3-C3H5)Cl] and [(CH2─C(Me)═C(Me)─P(Mes*))2PdCl2], respectively. All the complexes were fully characterized spectroscopically and structurally.
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