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Updated: Aug 25, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Synthesis and reactivity of cyclopentadienyl-phenoxide samarium complexes for proton-coupled electron transfer in
Taichi Mitsumoto1, Takahiro Nakama1, Sei Yoneda1
1Department of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan. ynishiba@g.ecc.u-tokyo.ac.jp.
Abstract:
Cyclopentadienyl-phenoxide samarium complexes were synthesized, and their reactivity as a proton-coupled electron transfer (PCET) mediator was investigated in molybdenum-catalyzed ammonia formation. The samarium complexes, chelated by a 3,4-diphenylcyclopentadienyl-phenoxide ligand, mediated proton and electron transfer from a terminal proton source and reductant to molybdenum complexes through more than 130 catalytic cycles, resulting in efficient catalytic nitrogen fixation. The PCET-active Sm(II) intermediate was investigated using electrochemical measurements, NMR spectroscopy, and density functional theory (DFT) calculations. This study highlights the importance of developing samarium complexes as PCET catalysts for achieving sustainable, green ammonia synthesis.
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