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Tantalum ureate complexes for photocatalytic hydroaminoalkylation.

Han HaoManfred ManßenLaurel L Schafer
Published in: Chemical science (2023)
Using a tantalum ureate pre-catalyst, photocatalytic hydroaminoalkylation of unactivated alkenes with unprotected amines at room temperature is demonstrated. The combination of Ta(CH 2 SiMe 3 ) 3 Cl 2 and a ureate ligand with a saturated cyclic backbone resulted in this unique reactivity. Preliminary investigations of the reaction mechanism suggest that both the thermal and photocatalytic hydroaminoalkylation reactions begin with N-H bond activation and subsequent metallaaziridine formation. However, a select tantalum ureate complex, through ligand to metal charge transfer (LMCT), results in photocatalyzed homolytic metal-carbon bond cleavage and subsequent addition to unactivated alkene to afford the desired carbon-carbon bond formation. Origins of ligand effects on promoting homolytic metal-carbon bond cleavage are explored computationally to support enhanced ligand design efforts.
Keyphrases
  • room temperature
  • visible light
  • reduced graphene oxide
  • highly efficient
  • ionic liquid
  • transition metal
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  • metal organic framework