Synthesis, characterization, and photochemistry of Ru2(II,III) complexes of chalcogen oxides

We describe the synthesis, characterization, and photochemistry of a pair of Ru2(II,III) complexes featuring dibenzochalogen oxide ligands. Photolysis effects cleavage of the chalcogen–oxygen bond and oxygen atom transfer to phosphines is observed. These results expand the family of potential metal–oxo photoprecursors. [Display omitted] •Synthesis and characterization of O-bound chalcogen oxide ligands to Ru2(II,III) complexes.•Demonstration of E–O photoactivation and oxygen-atom transfer photochemistry.•Provides new platforms for tunable, predictable photogeneration of reaction metal–oxygen species. We describe the synthesis, characterization, and photochemistry of a pair of Ru2(II,III) complexes featuring dibenzochalogen oxide ligands, which were prepared as potential photoprecursors for Ru2 oxo photochemistry. Treatment of [Ru2(chp)4H2O]BF4 with either dibenzo[b,d]thiophene 5-oxide (DBTO) or dibenzo[b,d]selenophene 5-oxide (DBSeO) affords [Ru2(chp)4DBTO]BF4 or [Ru2(chp)4DBSeO]BF4, respectively, in which the dibenzochalcogen oxide ligands display coordination through oxygen (chp = 6-chloro-2-oxypyridinate). Both dibenzochalcogen oxide complexes are characterized by NMR, UV-vis, and IR spectroscopies as well as X-ray crystallography. Photolysis (λ = 300 nm) of [Ru2(chp)4DBTO]BF4 and [Ru2(chp)4DBSeO]BF4 effects cleavage of the chalcogen–oxygen bond and oxygen atom transfer to phosphine additives is observed. These results expand the family of potential metal–oxo photoprecursors and demonstrate new opportunities in the photochemical synthesis of reactive metal–oxygen complexes.