The reaction of 1-phenyl-2-lithio-3,4-dimethylphosphole with W(CO) 6 at -90 C followed by methyl triflate at room temperature gives the complex [(phosphol-2-yl)methoxycarbene]pentacarbonyltungsten (1). This complex reacts with sulfur to give the corresponding complex [methyl (phosphol-2-yl)thiocarboxylate]pentacarbonyltungsten (2), in which tungsten has migrated from the carbene to phosphorus. The reaction of 3 with alkynes at 90 C gives the corresponding phospholene-annelated cyclopentenones 5 without the need for a nickel catalyst. In one case, an intermediate vinylketene rearranges by an intramolecular Diels-Alder reaction to give the tricyclic compound 6. All of the products have been characterized by X-ray crystal structure analysis. © 2013 American Chemical Society.