Tungsten-Catalyzed Alkyne Metatheses in Transition-Metal Coordination Spheres:  Versatile New Syntheses of Metallamacrocycles

The title reaction (10−15 mol % of (<i>t</i>-BuO)<sub>3</sub>W(⋮C-<i>t</i>-Bu), chlorobenzene, 80 °C) is applied to octahedral and square-planar 18- and 16-valence-electron rhenium, ruthenium, and platinum complexes with <i>cis</i>- or <i>trans</i>-Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>6</sub>C⋮CCH<sub>3</sub> ligands. NMR analyses show ca. 90−70% educt conversions, and 17-membered diphosphine chelates have been isolated in 59−47% yields and crystallographically characterized.