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Published on: August 12, 2019
Dinitrogen Binding and Functionalization from a Low-Coordinate Alkynyliron Complex
Samuel M Bhutto1, Brandon Q Mercado1, Patrick L Holland1
1Department of Chemistry, Yale University, New Haven, Connecticut 06511, United States.
Abstract:
Alkynyl complexes of low-coordinate transition metals offer a sterically open environment and interesting bonding opportunities. Here, we explore the capacity of iron(I) alkynyl complexes to bind N2 and isolate a N2 complex including its X-ray crystal structure. Silylation of the N2 complex gives an isolable, formally iron(IV) complex with a disilylhydrazido(2-) ligand, but natural bond orbital analysis indicates that an iron(II) formulation is preferable. The structure of this compound is similar to an earlier reported phenyl complex in which phenyl migration forms a new N-C bond, but the alkynyl group does not migrate. DFT calculations are used to test the possible reasons why the alkynyl is resistant to migration, and these show that the large Fe-C bond energy in the alkynyl complex is a factor that could contribute to the lack of migration.
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