Dinitrogen Activation by Heteronuclear Metal Carbide Cluster Anions FeTaC2-: A 5d Early and 3d Late Transition Metal
Li-Hui Mou1,2,3, Yao Li4,2,3, Zi-Yu Li1,3
1State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Abstract:
Cleavage of the strong N≡N bond has long been a great challenge for energy-efficient dinitrogen (N2) fixation; thus a reasonable design of reactive species to activate N2 under mild conditions is highly desirable and meaningful. Herein a novel N2 activation strategy of combining 5d early (E) and 3d late (L) transition metals (TMs) is proposed, which is verified by the facile and complete N≡N cleavage via the polarized Fe-Ta bond in gas-phase cluster FeTaC2-. The efficient N≡N cleavage benefits from an electronic-level design of highly strengthened donor-acceptor interactions, in which the 5d-ETM (Ta) mainly pushes electrons from occupied 5d-orbitals to N2 π*-orbitals while the 3d-LTM (Fe) simultaneously pulls electrons from N2 σ/π-orbitals to its unoccupied 3d-orbitals. Through employing 5d-ETM and 3d-LTM to play their respective roles, this work provides a new and versatile idea for activating the inert N≡N bond and inspires relevant design of TM-based catalysts.
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