Photo-oxidation of metal carbynes

Photo-oxidation of the metal carbyne complexes (η-C⁵H₅)L₁L₂MCR (MMo, W; L₁, L₂CO, P(OMe)₃; R ≡ phenyl, cyclopropyl) generates radical that are extremely reactive. Depending on the reaction conditions, either the oxidized species exhibit the ligand exchange and atom abstraction processes typical of metal radicals, or the carbyne ligands undergo a series of highly unusual rearrangement to yield organic products. For the cyclopropyl carbynes (η⁵-C₅H₅)P(OMe)₃](CO)MC(c-C₃H₅), photo-oxidation in the absence of added ligands results in the formation of cyclopentenone. When substituents are present on the cyclopropyl ring, single regioisomers or stereoisomers of the resulting cyclopentenones are produced.