Ring-opening of tetrahydrofuran with PCl3 catalysed by an ortho-xylidenedizinc complex

The reaction of 1,2-o-xylyl dichloride with activated zinc in THF gives the organozinc compound [(μ-o-xyl)Zn2Cl2(THF)4], 1, where xyl = (2-methanidylphenyl)methanide. The compound is stable in the solid state but undergoes a slow decomposition in solution to generate the μ4-oxo cluster [(μ-o-xyl)2Zn4(μ-Cl)2(μ4-O)(THF)4], 3, which has been characterised in the solid state by single-crystal X-ray techniques. The organozinc complex 1 catalyses the ring-opening of THF in the presence of PCl3 to give a mixture of the two compounds [Cl(CH2)4O]PCl2 and [Cl(CH2)4O]2PCl.