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Abstract
The zirconacyclocumulenes 1a (R = CH3) and 1b (R = Ph) were prepared by isomerization of bis(propynyl)ZrCp2 or bis(phenylethynyl)ZrCp2, respectively, catalyzed by B(C6F5)3 (6 mol %). The compounds 1 added PCl3, PhPCl2, or Ph2PCl with cleavage of only one zirconium−carbon single bond. Chloride was added to zirconium and the remaining −PCl2, −P(Ph)Cl, or −PPh2 moiety attached at the distal β-carbon atom of the strained ZrC4R2 metallacycle to yield the respective ring-opened Zr/P-substituted enyne systems (5−7). The complexes 7a and 7b (both with −PPh2) and 6b (with −P(Ph)Cl) were characterized by X-ray diffraction.
Published Version
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