Flash Communication: Carbanion Translocation via Intramolecular 1,2-Proton Transfer for One-Carbon Expansion of Lanthanide Metallacycles
Abstract
Intramolecular hydrogen transfer represents one of the most fundamental and ubiquitous processes in both chemical and biological transformations. Here, we introduce a rare intramolecular 1,2-proton transfer within lanthanide metallacycles proceeds without external shuttles. The transformation converts five-membered lutetacyclopentenes into six-membered rings through a formal 1,2-proton transfer achieved via sequential 1,5- and 1,4-proton shifts. DFT calculations reveal that the Lu–C bond acts as an internal proton relay, preorganizing the transfer trajectory and lowering the barrier. Isolation of a ligand-stabilized intermediate further substantiates the proposed stepwise mechanism.
Fields of Study & Subjects
Organometallic Complex Synthesis and Catalysis
Synthesis and characterization of novel inorganic/organometallic compounds
Inorganic and Organometallic Chemistry
Publication details
- Journal / source
- Organometallics
- Volume
- 45
- Issue
- 5
- Pages
- 534–537
- Publication date
- 23 February 2026
- Language
- EN