Surface nitrides have been identified as key intermediates in various industrial processes, like the Haber-Bosch synthesis of ammonia and Ostwald synthesis of nitric acid. Synthetic chemists have generated several late-metal, bimetallic bridging nitrides that may be thought of as mimics of these surface species, but bridging nitrides between low-valent metals are rare and those between high-valent metals exhibit little reactivity. This work has similarly been limited by the lack of control in structural rearrangements of molecular complexes when mimicking surface chemistry. Herein, we report a novel di-iron bridging nitride species [(3PDI2)Fe2(μ-N)(PMe3)2][OTf] (PDI=2,6-pyridyl-diimine, OTf=trifluoromethanesulfonate) supported by a dinucleating ligand, 3PDI2, that allows for both geometric flexibility through non-rigid alkyl linkers and electronic flexibility through redox-active PDI fragments. This presentation will show that the bridging nitride in this species performs hydrogen atom transfer (HAT) from Ph2PH to form two N–H bonds, concomitant with folding of the macrocycle as the complex transforms into a bridging amide species. Silane activation by formal insertion of the nitrido unit into a Si–H bond (PhSiH3: BDFESi–H=90.3 kcal/mol) has also been observed. Kinetic studies have been used to shed light on the mechanisms of these transformation and will be discussed in this session.

Mechanistic study of hydrogen atom transfer and Si–H addition to a diiron-bridging nitride complex

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.