Visible-Light-Induced Bond Homolysis in Titanacyclopentadienes for the Catalytic Cyclodimerization of Internal Alkynes.

ABSTRACT: Ligand-to-metal charge transfer (LMCT) processes offer significant potential in photochemical synthesis but remain comparatively underdeveloped, relative to metal-to-ligand charge transfer (MLCT) pathways. Titanium organyls are particularly promising in this context, enabling the direct generation of carbon-centered radicals. However, reports on their photochemistry have remained scarce. Herein, we present the visible-light-induced homolytic cleavage of a Ti-C bond in a titanacyclopentadiene complex supported by a bulky pyridine-diamido ligand. The resulting biradicaloid undergoes a selective skeletal rearrangement via a H atom shift to form a titanacyclopentene. This stoichiometric transformation was translated into a novel catalytic cyclodimerization of internal alkynes. With 2-butyne, t

SUBMITTER: Heldner ML 

PROVIDER: S-EPMC12532294 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature